annual report 2019 · 2020. 3. 19. · 7. processing of feeble magnetic materials under a magnetic...
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Faculty of Environmental Sciences Department of Applied Chemistry for Environment
Graduate School of Environmental Sciences
Department of Applied Chemistry for Environment
Annual Report 2019
Index
Reports from Research Groups
Kawakami Laboratory ▪▪▪▪▪ 1
Masuda Laboratory ▪▪▪▪▪ 7
Asayama Laboratory ▪▪▪▪▪ 9
Kubo Laboratory ▪▪▪▪▪ 11
Setaka Laboratory ▪▪▪▪▪ 14
Kanamura Laboratory ▪▪▪▪▪ 16
Kajiwara Laboratory ▪▪▪▪▪ 19
Takagi Laboratory ▪▪▪▪▪ 21
Uchiyama Laboratory ▪▪▪▪▪ 25
Shishido Laboratory ▪▪▪▪▪ 29
Shudo Laboratory ▪▪▪▪▪ 32
Colloquium ▪▪▪▪▪ 33
Reports from Research Groups
Kawakami Laboratory
■MembersHiroyoshi KAWAKAMIProfessor / Dr. Eng.Polymer Chemistry, Functional Polymers, NanofiberEngineering, Biomaterials, Epigenetics Engineering, FreeRadical ScienceRm. 9-638, +81-42-677-1111 Ext. [email protected]
Masafumi YAMATO Associate Professor / Dr. Eng. Polymer Science, Magneto-Science Rm. 9-137, +81-42-677-1111 Ext. 4837 [email protected]
Kiyoshi SATO Associate Professor / Dr. Eng. Synthetic Organic Chemistry, Molecular Recognition, Heterocyclic Chemistry, Physical Organic Chemistry Rm. 9-349, +81-42-677-1111 Ext. 4886 [email protected]
Manabu TANAKA Associate Professor / Dr. Eng. Polymer Chemistry, Polymer Energy Materials, Fuel Cells, Secondary Batteries, Nanofibers, Polymer Membranes Rm. 9-639, +81-42-677-1111 Ext. 4586 [email protected]
Doctor’s course - 2 Master’s course - 19 Bachelor 4 - 8
■Outlines of the Research
1. Study of Functional Polymer MembraneHiroyoshi KAWAKAMI, Masafumi YAMATO,Manabu TANAKA
Membrane-based gas separations have tremendous potential as energy-efficient alternatives or removal material of greenhouse gasses, such as carbon dioxide (CO2). Recently, we have reported that novel composite membranes composed of the fluorinated polyimide or polymers of intrinsic microporosity (PIM) and surface-modified silica nanoparticles exhibit high gas permeability and selectivity.
In this year, we found that the expansion of the nano-space which was formed on the surface of silica nanoparticles leads to an increase in gas permeability of composite membranes. The temperature dependence of the composite membrane containing surface-modified nanoparticles was also clarified. We have also started research on the development of composite membranes with asymmetric structures.
Figure 1. Enhancement of gas permeability by expansion of nano-space.
2. Study of Polymer Electrolyte MembraneHiroyoshi KAWAKAMI, Manabu TANAKA
Polymer electrolyte fuel cells have attracted much attention as clean and sustainable energy systems. We have reported composite polymer electrolyte membranes based on phytic acid (Phy)-doped polybenzimidazole nanofibers (PBINF) showed outstanding fuel cell performances under low relative humidity conditions.
In this year, we fabricated novel polymer composite membranes containing proton conductive nanofibers that have proton conductivity inside nanofibers, inter-connected structures to construct continuous proton conductive pathway, and surface-modified structures with acid and/or zwitterion molecules.. The novel polymer composite membranes showed higher proton conductivity than the conventional composite membranes, especially under low humidity conditions, which are assumed as future fuel cell operation conditions.
Figure 2. Approaches to improve proton conductivity on the nanofiber composite membranes.
3. Study of Electrospun NanofibersHiroyoshi KAWAKAMI, Manabu TANAKA
Recently, nano-scale fibers prepared through an electrically charged jet of polymer solution/melt (electrospinning) have received a lot of attention. Nanofibers have several inherent characteristics including high surface area, unique optical and physicochemical properties originated from the nano-size, and alignment of polymer chains in the nanofibers. The diameter of nanofiber is one of the most important factors to effect on such unique characteristics. Ultrafine nanofibers with their diameters less than 50 nm were also obtained.
In this year, we mainly focused on the fabrication of the polymer composite membranes containing polar crystalline poly(vinylidene difluoride) nanofibers for the secondary battery applications. The novel lithium ion conductive nanofiber composite membranes showed high lithium ion conductivity and good charge-discharge properties.
Figure 3. Schematic illustration of the lithium ion battery using the lithium ion conductive polymer nanofiber composite membrane.
4. Design of Multi-electron Redox CatalystsHiroyoshi KAWAKAMI, Kiyoshi SATO
② NF連結性向上
① NF内部もプロトン伝導に活用
③ 表面プロトン伝導層の拡大
① Utilization of inside nanofiber
③ Surface-modification
② Connected
1
Reports from Research Groups
Native metallo-enzymes facilitate various types of chemical reactions under mild conditions in water. Thus, an artificial metal complex as a bioinspired metallo-enzyme has application potential for wide field of chemistry such as energy chemistry and medicinal chemistry. In this year, we have prepared a novel dinuclear metalloporphyrin bearing six phenolic OH substituents spatially closed to the metal centers. The metal complex acts as a proton-coupled multi-electron catalysis for electrochemical CO2 reduction by an efficient combination of the metal centers and OH groups. Figure 4. Proton-coupled multi-electron redox catalyst for electrocatalytic CO2 reduction. 5. Study of Epigenetics Engineering Hiroyoshi KAWAKAMI, Kiyoshi SATO, Riku KUBOTA
The development and maintenance of an organism is orchestrated by a set of chemical reactions that switch parts of the genome off and on at strategic times and locations. Epigenetics is the study of these reactions and the factors that influence them.
In this year, we have prepared novel anionic polymers for the artificial epigenetic control of the chromatin conformations. The anionic oligo- and poly-peptides successfully delivered to nucleus and show regulation of gene expressions. We also prepared a liposome nanocarrier capable of induction of mitophagy of damaged mitochondria to suppress cellular senescence. These biomaterials will provide new treatment strategies for acquired diseases caused by epigenomic modifications and regenerative therapy (adoptive cellular immunotherapy). Figure 5. Epigenetic gene expression control by chromatin conformations. 6. Study of Free Radical Control by Artificial Enzyme Hiroyoshi KAWAKAMI, Kiyoshi SATO, Riku KUBOTA
Superoxide dismutase (SOD) or catalase (CAT) are well known to efficiently eliminate superoxide radicals or hydrogen peroxide as the most important antioxidants. We demonstrated that a water-soluble cationic Mn-porphyrin with SOD activity or catalase activity exhibited anticancer activity as well as antioxidative activity.
In this year, we have prepared a cationic manganese N-confused porphyrin (MnNCP) as a coreductant-free catalyst for ONOO- disproportionation. The pyridinium-appended tetracationic MnNCP showed a higher ONOO- eliminating activity than that of previous reported metal porphynoids under physiological conditions without coreductants. Furthermore, synthesis of MnNCP dimer, expected a multiple antioxidant activity, is now under investigation. Figure 6. Cationic-N-confused Mn-porphyrin (MnNCP) with peroxynitrite eliminating activity. 7. Processing of feeble magnetic materials under a magnetic field Masafumi YAMATO Controls of higher-order structure of feeble magnetic materials by using a magnetic field have been studied in order to improve some properties and to reveal new functions of the materials. In this year, we focused on research of anisotropic organic / inorganic hybrid gels. The plane orientation of the clay in the nano composite gel was achieved by using a rotating magnetic field. The resulting gel showed anisotropy in Young's modulus and swelling. We succeeded in producing the nanocomposite gels with mechanical anisotropy. Figure 7. Schematic drawing of plane orientation of clay by rotating magnetic field and stress-strain curves of nanocomposite gels preparing in a rotating magnetic field. ■Papers with Peer Review 1. Manjit Singh Grewal, Manabu Tanaka, Hiroyoshi
Kawakami, "Fabrication and characterizations of soft and flexible Poly(dimethylsiloxane)-incorporated network polymer electrolyte membranes", Polymer, 186,122045 (2020).
2. Yuki Kudo, Hiroto Mikami, Manabu Tanaka, Tadayuki Isaji, Kazutoshi Odaka, Masafumi Yamato, Hiroyoshi Kawakami, "Mixed matrix membranes comprising a polymer of intrinsic microporosity loaded with surface-modified non-porous pearl-necklace nanoparticles", Journal of Membrane
N
N N
N
N+
HO OH
OH
OH
HO OH
Fe
Rotating MF
2
Reports from Research Groups
Science, 597, 117627 (2020). 3. Naoki Sakaguchi, Manabu Tanaka, Masafumi Yamato,
Hiroyoshi Kawakami, "Superhigh CO2-Permeable Mixed Matrix Membranes Composed of a Polymer of Intrinsic Microporosity (PIM-1) and Surface-Modified Silica Nanoparticles", ACS Applied Polymer Materials, 1, 2516-2524 (2019).
4. Tsukasa Watanabe, Yuta Inafune, Manabu Tanaka, Yasumasa Mochizuki, Futoshi Matsumoto, Hiroyoshi Kawakami, "Development of all-solid-state battery based on lithium ion conductive polymer nanofiber framework", Journal of Power Sources, 423, 255-262 (2019).
5. Manjit Singh Grewal, Manabu Tanaka, Hiroyoshi Kawakami, "Free-standing polydimethylsiloxane-based cross-linked network solid polymer electrolytes for future lithium ion battery applications", Electrochimica Acta, 307, 148-156 (2019).
6. Manjit Singh Grewal, Manabu Tanaka, Hiroyoshi Kawakami, "Bifunctional poly(ethylene glycol) based crosslinked network polymers as electrolytes for all-solid-state lithium ion batteries", Polymer International, 68, 684-693 (2019).
7. Taku Ibaraki, Manabu Tanaka, Hiroyoshi Kawakami, "Fast surface proton conduction on acid-doped polymer nanofibers in polymer electrolyte composite membranes", Electrochimica Acta, 296, 1042-1048 (2019).
8. Kosuke Chikuma, Kohei Arima, Yutaro Asaba, Riku Kubota, Shoichiro Asayama, Kiyoshi Sato, Hiroyoshi Kawakami, "The potential of lipid-polymer nanoparticles as epigenetic and ROS control approaches for COPD", Free Radical Research, 1-12 (2019).
9. Riku Kubota, Shoichiro Asayama, Hiroyoshi Kawakami, "Catalytic antioxidants for therapeutic medicine", Journal of Materials Chemistry B, 7, 3165-3191 (2019).
10. Yuki Kobayashi, Sakura Taneichi, Hiroyoshi Kawakami, Yoichi Negishi, Shoichiro Asayama, "Plasmid DNA Mono-Ion Complex for in Vivo Sustainable Gene Expression", ACS Omega 4, 11464–11471 (2019).
11. Fuminori Ito, Hidetaka Yamada, Kiyoshi Kanamura & Hiroyoshi Kawakami, "Preparation of Biodegradable Polymer Nanospheres Containing Manganese Porphyrin (Mn-Porphyrin)", Journal of Inorganic and Organometallic Polymers and Materials, 29, 1010–1018 (2019).
■Books 1. Manabu Tanaka, Hiroyoshi Kawakami, “Nanofibers:
Fabrication and Applications”, Technical Information Institute (Tokyo, Japan), p263-269 (2019). (in Japanese)
2. Manabu Tanaka, Hiroyoshi Kawakami, “Development of Surface-modified Nanofiber Composite Membranes for Low-humidified Operation”, Fuel Cell, 19, 1, p29-33 (2019) (in Japanese)
3. Hiroto Mikami, Takuya Muramoto, Eiko Ito, Manabu Tanaka, Masafumi Yamato, Hiroyoshi Kawakami, “Fabrication and Characterizations of Polymers of Intrinsic Microporosity Gas Separation Membrane for High Gas Permeability, Proceeding of 27th Japan Polyimide Conference, p38-41 (2019) (in Japanese)
4. Masafumi Yamato , ”Development of High Thermal Conductivity Materials-For Further Improvement of Thermal Conductivity-(Chapter 3, Section 6, Filler
Orientation Control Technology Using Magnetic Field)”, Technical Information Institute (Tokyo, Japan), 132-140 (2019). (in Japanese)
5. Masafumi Yamato, Kohki Takahashi,, Study in interaction between organic molecules and clay using magnetic alignment, 2018 Annual report of high field laboratory for superconducting materials in institute for materials research at Tohoku university,p.p. 158-159 (2019) (in Japanese)
■Invited Lectures 1. Masafumi Yamato, Thermal and magnetic properties of
polymer, 2019Basic seminar of polymer science for young engineers, Oct. 2019 Hiratsuka, Japan (in Japanese).
2. Masafumi Yamato, Understanding the supercooling of crystalline polymers and controlling the orientation by magnetic field,25th Research meeting of Magneto-science Society of Japan, Dec. 2019, Tokyo Japan (in Japanese)
3. Manabu Tanaka, Development of Surface-modified Nanofiber Composite Membranes for Low-humidified Operation, The 26th Fuel Cell Symposium, May 2019, Tokyo Japan (in Japanese)
4. Manabu Tanaka, Fabrication and Battery Applications of Ion Conductive Polymer Nanofibers, Lecture at Kanagawa University, Sep. 2019, Yokohama Japan (in Japanese)
5. Manabu Tanaka, Development of Polymer Nanofiber Composite Membranes for Next-generation Fuel Cells, The 161st lecture meeting of Hydrogen Energy System Society of Japan, Jan. 2020, Tokyo Japan (in Japanese)
■Academic Meeting 1. Kosuke Chikuma, Kohei Arima, Riku Kubota, Kiyoshi Sato,
Hiroyoshi Kawakami, A novel approach by ROS inhibiton and HDAC2 activation for COPD treatment, The 9th Biennial Meeting of Society for Free Radical Research-Asia (Kyoto International Community House), P15, April 2019(in English)
2. M. Yamato, H. Kawakami,Study on gas permeation in surface-modified silica nanoparticle containing composite membrane with high gas permeability,41st annual meeting of membrane science of Japan, May 2019, Tokyo, Japan (in Japanease).
3. Motoki Nishizawa, Manabu Tanaka, and Hiroyoshi Kawakami, Enhancement of proton conductivity of composite electrolyte membrane by nanofiber containing polyvinylphosphonic acid, 39 th The Membrane Society of Japan, (Waseda University), P–16S (May 2019)
4. Mitsuki Ochiai, Manabu Tanaka, Hiroyoshi Kawakami,Secondary battery characteristics of Lithium ion conductive nanofiber composite membrane, 41th Annual Meeting on The Membrane Society of Japan, Waseda University, P-17S May 2019 (in Japanese)
5. Yu Matsuda, Manabu Tanaka, Hiroyoshi Kawakami. Lithium ion conductive characteristics of composite electrolyte membranes consisted of polymer nanofibers. 41th Annual Meeting of the Membrane Society of Japan (Waseda University), P–19S, May 2019 (in Japanese)
6. Xinming Qi, Manjit Singh Grewal, Manabu Tanaka, Hiroyoshi Kawakami, Lithium ion conductive characteristics of ionic liquid containing cross-linked polymer electrolyte membranes, 41th Annual Meeting of The Membrane Society of Japan (Waseda University), P-33S, May 2019 (in Japanese)
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Reports from Research Groups
7. Takahiro Miyazaki, Masafumi Yamato, Hiroyoshi Kawakami, Noriyuki Hirota, Adsorption behavior of NIPAm to clay, 41th The Membrane Society of Japan, (Waseda University), P-26S (May, 2019) (in Japanese)
8. M. Yamato, K. Komine, T. Miyazaki, H. Kawakami, Study in adsorption of NIPAm on clay using NMR and magneto birefringence measurements, 68th SPSJ annual meeting, May 2019, Osaka, Japan (in Japanease)
9. Manabu TANAKA, Takahiro OGURA, Hiroki HARADA, Motoki NISHIZAWA, Hiroyoshi KAWAKAMI, Fabrication and characterization of novel electrolyte composite membranes based on polymer nanofibers for fuel cell operation at unhumidified high temperature. The 68th SPSJ Annual Meeting (Osaka International Conference Center), May 2019 (in Japanese)
10. Mitsuki Ochiai, Shun Nakazawa, Manabu Tanaka, Hiroyoshi Kawakami, Evaluation of secondary battery characteristics of lithium salt-added nanofiber composite electrolyte membranes, The 68th SPSJ Annual Meeting (Osaka International Conference Center), 2H18, May 2019 (in Japanese)
11. Mitsuki Ochiai, Manabu Tanaka, Hiroyoshi Kawakami, Influence of nanofiber framework on lithium dendrite formation, The 68th SPSJ Annual Meeting (Nagoya International Conference Center), 1Pf084, May 2019 (in Japanese)
12. Yu Matsuda, Shun Nakazawa, Masahumi Yamato, Tanaka Manabu, Hiroyoshi Kawakami. Lithium ion conductive characteristics of n anofibers with spontaneous polarization. The 68th SPSJ Annual Meeting (Nagoya International Conference Center), 2H17, May 2019 (in Japanese)
13. Yu Matsuda, Manabu Tanaka, Hiroyoshi Kawakami. Lithium ion conductive characteristics of composite electrolyte membranes consisted of various polymer nanofibers. The 68th SPSJ Annual Meeting (Nagoya International Conference Center), 1Pe083, May 2019 (in Japanese)
14. Kazuma Komine, Masafumi Yamato, and Hiroyoshi Kawakami, Evaluation of N-isopropylacrylamide adsorbed on clay using NMR., 19-1 Research Group on Nuclear Magnetic Resonance (Tokyo University of Marine Science and Technology), P-04, May 2019.
15. Ayano Imai, Hiroto Mikami, Eiko Ito, Manabu Tanaka, Hiroyoshi Kawakami, Effect of chemical modification on CO2 permeability of polymer composite membranes containing surface-modified silica nanoparticles, The 36th International Conference of Photopolymer Science and Technology, Makuhari Messe, Japan, B1-02, June 2019 (in Japanese)
16. Kosuke Chikuma, Kohei, Arima, Riku Kubota, Kiyoshi Sato, Hiroyoshi Kawakami, COPD treatment by the synergistic effect of ROS elimination and HDAC2 activation, The 72nd Annual Meeting of Society for Free Radical Research JAPAN (Hokkaido Prefectural Citizens Activity Center), P-14, June 2019(in Japanese)
17. Ayano Imai, Hiroto Mikami, Manabu Tanaka, Masafumi Yamato, and Hiroyoshi Kawakami, Influence of surface-modified structures of silica nanoparticles on gas permeation properties of polymer composite membranes, The Annual Meeting of the Society of Fiber Science and Technology (Tower Hall Funabori), 2B06, June 2019(in Japanese)
18. Motoki Nishizawa, Manabu Tanaka, and Hiroyoshi Kawakami, Evaluation of Fuel Cell Characteristics of Composite Electrolyte Membrane with Polyvinylphosphonic Acid Containing Nanofiber, The Annual Meeting of the Society of Fiber Science and Technology, Japan(Tower Hall Funabori), 2P216 (June 2019)
19. Motoki Nishizawa, Takahiro Ogura, Manabu Tanaka, and Hiroyoshi Kawakami, Preparation of proton conductive nanofibers containing sulfonic acid and phosphonic acid and their application to fuel cells, The Annual Meeting of the Society of Fiber Science and Technology, Japan(Tower Hall Funabori), 3F02 (June 2019)
20. Mitsuki Ochiai, Shun Nakazawa, Manabu Tanaka, Hiroyoshi Kawakami, Preparation and evaluation of secondary battery using lithium salt-added nanofiber composite electrolyte, The Annual Meeting of the Society of Fiber and Technology (Tower Hall Funabori), 2B12, June 2019 (in Japanese)
21. Mitsuki Ochiai, Manabu Tanaka, Hiroyoshi Kawakami, Influence of nanofiber framework on lithium dendrite formation and application for secondary battery, The Annual Meeting of the Society of Fiber and Technology (Tower Hall Funabori), 1P219, June 2019 (in Japanese)
22. Yu Matsuda, Shun Nakazawa, Masahumi Yamato, Tanaka Manabu, Hiroyoshi Kawakami. Lithium ion conductive characteristics of nanofibers contained lithium salt. The Annual Meeting of The Society of Fiber and Technology (Tower Hall Funabori), 2B11, June 2019 (in Japanese)
23. Yu Matsuda, Manabu Tanaka, Hiroyoshi Kawakami. Lithium ion conductive characteristics of composite electrolyte membranes consisted of polymer nanofibers. The Annual Meeting of the Society of Fiber and Technology (Tower Hall Funabori), 2P215, June 2019 (in Japanese)
24. Risa Mitsuhashi, Riku Kubota, Kiyoshi Sato, Hiroyoshi Kawakami, Control of DNA methylation by epigenetics control carrier in cancer cell, 48th Medical macromolecular symposium, P3, July 2019, Tokyo, Japan (in Japanese)
25. Takeru Yamazaki, Kohei Arima, Riku Kubota, Kiyoshi Sato, Hiroyoshi Kwakami, Inhibition of ROS induced epithelial-to-mesenchymal transition by functional nano-particle, 48th Medical macromolecular symposium, P22, July 2019, Tokyo, Japan (in Japanese)
26. Y. Okazaki, M. Yamato, T. Kato,Construction of a spiral structure mimicking crustaceans using liquid crystal of cellulose nanocrystal,23rd symposium on liquid-crystalline chemistry, July 2019, Yokohama, Japan (in Japanese).
27. Takuya Muramoto, Manabu Tanaka, Masafumi Yamato, and Hiroyoshi Kawakami, Preparation and evaluation of surface-modified pearl-necklace nanoparticles containing PIM-1 composite membrane with high gas permeability, The 4th International Symposium on Hydrogen Energy‒based Society (Tokyo Metropolitan University), P-24, Aug. 2019
28. Xinming Qi, Hiroyoshi Kawakami, Manabu Tanaka, Lithium ion conductive characteristics of cross-linked polymer electrolyte membranes containing ionic liquid, The 4th International Symposium on Hydrogen Energy‒based Society, TMU (Aug 2019)
29. Motoki Nishizawa, Risa Sakaguchi, Manabu Tanaka, and Hiroyoshi Kawakami, Fabrication and characteristic evaluation of composite electrolyte membranes containing proton conductive polymer nanofibers for fuel cells, International Seminar on Green Energy Conversion 2019,
4
Reports from Research Groups
(Yamanashi University), (August, 2019) 30. Yu Matsuda, Manabu Tanaka, and Hiroyoshi Kawakami,
Lithium Ion Conductive Characteristics of composite Electrolyte Membranes Consisted of Polymer Nanofibers, International Seminar on Green Energy Conversion 2019, (Yamanashi University), (August, 2019)
31. Manabu TANAKA, Takahiro OGURA, Motoki NISHIZAWA, Moeri SHIMIZU, Hiroyoshi KAWAKAMI, Development of Nanofiber Composite Membranes Consisted of Non-Sulfonated Polymer Matrix for Reduction of Fuel Cell Cost, The 68h Symposium on Macromolecules (Fukui University) 2I10 (September 2019) (in Japanese)
32. Yu Matsuda, Mitsuki Ohiai, Syun Nakazawa, Manabu Tanaka, Masahumi Yamato, HIroyoshi Kawakami. Ion conductive characteristics and secondary battery application of composite electrolyte membranes consisted of nanofibers containing lithium salts. 68h Symposium on Macromolecules (Hukui University) 1I15 (September 2019) (in Japanese)
33. Yu Matsuda, Manabu Tanaka, Masahumi Yamato, Hiroyoshi Kawakami. Lithium ion conductive characteristics of composite electrolyte membranes consisted of nanofibers with polar groups. 68h Symposium on Macromolecules (Hukui University) 2Pf070 (September 2019) (in Japanese)
34. Minami Kawai, Riku Kubota, Kiyoshi, Sato, Hiroyoshi Kawakami, Formation of inclusion complexes between metalloporphyrins and cucurbituril, 69th Conference of Japan Society of Coordination Chemistry (Nagoya University, Higashiyama campus), 1PF-003 (September 2019)
35. M. Yamato, T. Nakaoji, K. Komine, H. Kawakami, Mechanical Anisotropy of MMT-NC Gel Prepared in Magnetic Field, 80th JSAP Autumn Meeting, Sep. 2019, Sapporo, Japan (in Japanease).
36. M. Yamato, K. Komine, T. Miyazaki, H. Kawakami, Study in adsorption of NIPAm on Montmollironite using magneto birefringence measurements and quantitative NMR measurement, the 43rd Annual Conference on MAGNETICS in Japan, Sep. 2019, Kyoto, Japan (in Japanease).
37. S. KAJIYAMA, M. NAKAYAMA, A. KUMAMOTO, M. YAMATO, Y. IKUHARA, T. KATO, Morphological and Orientational Control of Liquid-Crystalline Colloidal Particles, Japanese Liquid Crystal Conference 2019, Sep. 2019, Tsukuba, Japan (in Japanese)
38. M. Yamato, T. Miyazaki, H. Kawakami, Measurement of magneto-birefringence of clay dispersion containing NIPAM, 12th Annual Meeting of the Magneto-Science Society of Japan, Nov. 2019, Nagaoka, Japan (in Japanease).
39. Kosuke Chikuma, Kohei, Arima, Kiyoshi Sato, Hiroyoshi Kawakami, Development of mitophagy-induced nanocarriers for the suppression of cellular senescence, The 57th Annual Meeting of the Japanese Society for Artificial Organs (Osaka International Convention Center), YP05-5, November 2019(in Japanese)
40. Yu Matsuda, Mitsuki Ohiai, Manabu Tanaka, Masahumi Yamato, HIroyoshi Kawakami, Evaluation of all-solid-state secondary battery composed of lithium salt-containing nanofibers, Membrane Symposium 2019, Osaka, (November, 2019)
41. Manabu Tanaka, Takahiro Ogura, Motoki Nishizawa, Moeri
Shimizu, Hiroyoshi Kawakami, Fabrication and Evaluation of Proton Conductive Nanofiber Composite Membranes Utilizing Non-sulfonated Polymer Matrix, The 60th Battery symposium, Kyoto International Conference Center, 1C04 (November, 2019)
42. Yuta Inafune, Mitsuki Ochiai, Yu Matsuda, Manabu Tanaka, Hiroyoshi Kawakami, Fabrication and evaluation of all-solid-state secondary batteries consisted of lithium salt-containing PVDF nanofiber composite polymer electrolyte membranes, The 60th Battery symposium, Kyoto International Conference Center, 3F23 (November, 2019)
43. Yu Matsuda, Mitsuki Ohiai, Manabu Tanaka, Masahumi Yamato, HIroyoshi Kawakami. Ion conductive mechanism analysis and all-solid-state battery application of composite polymer electrolyte membranes consisted of nanofibers containing lithium salts. The 60th Battery Symposium in Japan, Japan (Kyoto International Convention Center), (November 2019) (in Japanese)
44. Wataru Murata, Yuta Inafune, Manabu Tanaka, Hiroyoshi kawakami, Fabrication and evaluation of composite polymer electrolyte membranes based on lithium ion conductive PEO-grafted polyimide nanofibers, 27th symposium of polyimide and Aromatic polymer, Tokyo institute of Technology, Japan, P18 (November, 2019) (in Japanese)
45. Takahiro Miyazaki, Masafumi Yamato, Hiroyoshi Kawakami, Hirota Noriyuki, Adsorption behavior analysis using in-situ magneto-birefringence and quantitative NMR, 87th Musashino area polymer association, (Tokyo Metropolitan University), Poster (November, 2019) (in Japanese)
46. Takeru Yamazaki, Kiyoshi Sato, Hiroyoshi Kawakami, Regulation of the transition to cancer stem cells by nanoparticles exhibiting antioxidant and epigenetic control activities, The 41st Annual Meeting of the Japanese Society for Biomaterials, Tsukuba International Congress Center, P108, (November, 2019) (in Japanese)
47. Kazuma Komine, Takashi Nakaozi, Masafumi Yamato, and Hiroyoshi Kawakami, Mechanical properties of MMT-NC gel prepared in rotating magnetic field, 14th Annual Meeting of the Magneto-Science Society of Japan (City Hall Plaza Aore Nagaoka), P-25, November 2019.
48. Takuya Muramoto, Manabu Tanaka, Masafumi Yamato, and Hiroyoshi Kawakami, Preparation and evaluation of gas permeation properties of PIM-1 composite membranes containing surface-modified pearl-necklace silica nanoparticles, The 57th Annual Meeting (Tokyo University of Marine Science and Technology), P-10, Dec. 2019
49. Hiroki Harada, Manabu Tanaka, Hiroyoshi Kawakami, Fabrication and fuel cell characterizations of composite electrolyte membranes composed of proton conductive nanofibers modified with zwitterion for high proton conductivity at high temperature and low humidity, The 57th Annual Meeting of Polymer and Water (Tokyo University of Marine Science and Technology), P-11, Dec. 2019
50. Ayano Imai, Naoki Sakaguchi, Manabu Tanaka, Masafumi Yamato, and Hiroyoshi Kawakami, Gas Permeation Properties of PIM-1 Composite Membranes Containing Surface-modified Silica Nanoparticles, CEMSupra (Tokyo University Ito International Research Center) , December 2019
51. Mitsuki Ochiai, Manabu Tanaka, Hiroyoshi Kawakami,
5
Reports from Research Groups
Property Evaluation of Lithium Salt-containing Polymer Nanofiber Composite Electrolyte Membrane and Lithium Ion Secondary Battery Characteristics, CEMS International Symposium on Supramolecular Chemistry & Functional Materials 2019 (CEMSupra 2019), Tokyo, P-60 (December, 2019)
52. Yoshihiro HOSOKAWA, Kohei MOCHIZUKI, Masanari NAKAYAMA, Akihito KUMAMOTO, Yuichi IKUHARA, Masafumi YAMATO, Taiki HOSHINO, Takashi KATO, Liquid-Crystalline Inorganic/Organic Nano-Hybrids Obtained through Biomineralization-Inspired Processes, the 16th Pacific Polymer Congress, Dec. 2019, Suntec, Singapore,
53. Takahiro Miyazaki, Masafumi Yamato, Hiroyoshi Kawakami, Hirota Noriyuki, Study in Adsorption behavior of organic molecules to clay using *in-situ* magneto-birefringence and quantitative NMR, The 67th JSAP Spring Meeting, (Sophia University), 14p-PA1-2 (March, 2020) (in Japanese)
54. Takashi Nakaoji, Masafumi Yamato, Hiroyoshi Kawakami, Mechanical and optical properties of hydrogels cross-linked physically by clays, 25th Meeting of Magneto-Science Society of Japan 2019 (Nihon University), P4 (December, 2019)
55. Kosuke Chikuma, Kiyoshi Sato, Hiroyoshi Kawakami, Consideration of suppression of cellular senescence by functional nano-carrier inducing mitophagy, The 19th Congress of Japanese Society for Regenerative Medicine (Pacifico Yokohama), March 2020(in Japanese)
56. Shiori Higashi, Takuya Muramoto, Manabu Tanaka, Masafumi Yamato, Hiroyoshi Kawakami, Gas permeation properties of polymer membranes containing surface-modified pearl-necklace shaped nanoparticles, the SJEJ 85th Annual Meeting / IChES 2020 (Kansai University), PE302 (March, 2020) (in Japanese)
■Patents 1. JP2019-189994,A "Lithium ion conductive nanofiber,
Fabrication, Nanofiber assembly, Composite, Solid Polymer Electrolyte, and Lithium ion battery, Hiroyoshi Kawakami, Manabu Tanaka, Shun Nakazawa, Kaito Takenaka
2. JP2019-183379,A "Nanofiber, Nanofiber assembly, Composite membrane, Solid polymer electrolyte, and Lithium ion battery, Hiroyoshi Kawakami, Manabu Tanaka, Tsukasa Watanabe
■Awards 1. Prize for Encouragement, H30 Fuel Cell Development
Information Center (FCDIC), Manabu Tanaka, Development of Surface-modified Nanofiber Composite Membranes for Low-humidified Operation
2. Student poster award, The 68th SPSJ Annual Meeting, Mitsuki Ochiai, Manabu Tanaka, Hiroyoshi Kawakami, Influence of nanofiber framework on lithium dendrite formation
3. Student poster award, the 68th SPSJ Annual Meeting, Motoki Nishizawa, Manabu Tanaka, Hiroyoshi Kawakami, Enhancement of proton conductivity of composite electrolyte membrane by nanofiber containing polyvinylphosphonic acid
4. Student poster award, 2019 Annual Meeting on The Society
of Fiber Science and Technology, Japan, Mitsuki Ochiai, Shun Nakazawa, Manabu Tanaka, Hiroyoshi Kawakami, Influence of nanofiber framework on lithium dendrite formation and application for secondary battery.
5. Student poster award, 2019 Annual Meeting on The Society of Fiber Science and Technology, Japan, Yu Matsuda, Manabu Tanaka, Hiroyoshi Kawakami. Lithium ion conductive characteristics of composite electrolyte membranes consisted of polymer nanofibers.
6. Best Poster Award, The 57th Annual Meeting of the Japanese Society for Artificial Organs, Kosuke Chikuma, Kohei, Arima, Kiyoshi Sato, Hiroyoshi Kawakami, Development of mitophagy-induced nanocarriers for the suppression of cellular senescence
7. Student poster award, 27th symposium of polyimide and Aromatic polymer, Wataru Murata, Yuta Inafune, Manabu Tanaka, Hiroyoshi kawakami, Fabrication and evaluation of composite polymer electrolyte membranes based on lithium ion conductive PEO-grafted polyimide nanofibers
8. Student Poster Award, The 57th Annual Meeting of Polymer and Water, Hiroki Harada, Manabu Tanaka, Hiroyoshi Kawakami, Fabrication and fuel cell characterizations of composite electrolyte membranes composed of proton conductive nanofibers modified with zwitterion for high proton conductivity at high temperature and low humidity
6
Reports from Research Groups
Masuda Laboratory
■Members
Hideki Masuda
Professor/ Dr. Eng.
Electrochemistry, Nano Fabrication, Functional Electrode
Rm. 9-147, +81 426 77 2843
Takashi Takei
Associate Professor /Dr. Eng.
Solid surface chemistry, interface and colloid science
Rm. 9-136, +81 426 77 2822
Takashi Yanagisita
Associate Professor/ Dr. Eng.
Electrochemistry, Functional Metal Oxide Film
Rm. 9-140,+81 426 77 1111 (Ext. 4931)
Master’s course -10
Bachelor 4 -6
■Outlines of the Research
(1) Fabrication of Nanofilters by Electrochemical Process
Hideki MASUDA, Takashi YANAGISHITA
For the fabrication of ordered nanofilere membranes, we
have investigated anodization process of Al. The size and
interval of holes could be controlled by adjusting the anodization
conditions. Metal and semiconductor nanohole array structures
have been also fabricated using an anodic porous alumina as a
template. For the replacement of the ordered hole-array structure
with other materials we developed a two-step replication process
in which formation of a replicated negative and subsequent
preparation of a replicated positive give the nanohole structure
identical to that of mother structure of anodic orous alumina.
Metal (Au, Pt, Ni) and semiconductor (TiO2, ZnO, CdS)
nanohole arrays have been fabricated using the two-step process.
Detailed conditions for the precise replication were examined
experimentally, and new applications, such as optical devices
and detector for low energy ions, have been developed
SEM image of anodic porous alumina
(2) Preparation of Ordered Nanostructures by Nanoimprinting
Using Ordered Anodic Porous Alumina Molds
Hideki MASUDA, Takashi YANAGISHITA
Ordered pillar array and hole array patterns were fabricated
by nanoimprinting using anodic porous alumina. Patterned
surface prepared by this process could be used for the
antirefrection surface and surper hydrophobic surface.
(3). Fabrication of Enagy Devices Based on Ordered Anodic
Porous Alumina
Hideki MASUDA, Takashi YANAGISHITA
For the preparation of uniform sized nanoparticles, we have
introduced membrane emeulsification process using ordered
anodic porous alumina. The present process is simple and can be
used as a high-throughput process for forming monodispersed
nanoparticles of metal oxides. The monodispersed nanoparticles
prepared by this process will be useful as electrode active
materials in the Li ion batteries to improve the properties.
(4) Study of Self-ordering Mechanism of the Cell Arrangement
of Anodic Porous Alumina
Hideki MASUDA
Regularity of the holearray structure of the anodic porous
alumina which is used as mother template is important to
improve the regularity of the obtained metal and semiconductor
nanohole arrays. To improve the regularity of the holearray
structure of the anodic porous alumina, anodizing conditions
were explored, and self-ordering of the anodic oxide film was
newly discovered in sulfuric acid solution. The detailed
mechanism of the self-ordering of the anodic porous alumina is
currently being investigated.
(5)Evaluation of Pore Structures of Highly Ordered Porous
Alumina by Nitrogen Adsorption Method
Takashi Takei, Takashi Yanagishita, Hideki Masuda
The pore size distribution and surface area of highly ordered
porous alumina have been investigated by the nitrogen
adsorption method.
■Papers with Peer Review
1. T. Yanagishita, A. Kato, T. Kondo, and H. Masuda,
Preparation of Freestanding Tubular Alumina Through-
Hole Membranes by Two-Layer Anodization, Jpn. J. Appl.
Phys., 59, 038002 (2020).
2. T. Yanagishita, H. Awata, K. Kobayashi, T. Kondo, and H.
Masuda, Preparation of Polymer Nanofibers with
Controlled Diameters by Continuous Spinning Using
Ordered Anodic Porous Alumina as Spinneret, Chem. Lett.,
48, 86 (2019).
3. T. Yanagishita, G. Otain, H. Onomoto, T. Kondo, and H.
Masuda, One-Pod Preparation of Anodic Porous Alumina
Molds with Tapered Holes for Moth-Eye Structures by
Nanoimprinting, Jpn. J. Appl. Phys., 58, 068005 (2019).
■Reviews and Books
See the annual report in Japanese (6 articles)
■Invited Lectures
*International
1. T. Yanagishita, T. Kondo, and H. Masuda
Ordered Nanoporous Semiconductors with Controlled
Geometrical Structures by Anodization Process
235th Electrochemical Society Meeting, 2019/5,US.
2. H. Masuda
Fabrication of Highly Ordered Anodic Porous Alumina and
Its Functional Applications
3rd International Symposium on AST 2019,2019/6,Awaji.
7
Reports from Research Groups
3. T. Yanagihsita, T. Kondo, and H. Masuda
High Throughput Preparation of Through-Hole Membranes
with Ordered Hole Arrangement
3rd International Symposium on AST 2019,2019/6,Awaji.
*Domestic
See the annual report in Japanese (5 articles)
■Academic Meeting
*International
1. T. Kondo, R. Otsuki, K. Matsuo, T. Yanagishita, and H.
Masuda, Anisotropic Anode Etching of Al and its Optical
Application, 3rd International Symposium on AST2019, ,
2019/6, Awaji.
2. T. Kondo, T. Yanagishita, H. Masuda, Thermal Radiation
Control Structure Obtained by Anisotropic Anode Etching
of Al, ANZCOP 2019-SPIE, 2019/12,Australia.
*Domestic
See the annual report in Japanese (15 articles)
■Patents
See the annual report in Japanese (1 articles)
■Awards
See the annual report in Japanese (2 articles)
8
Asayama Laboratory
■Members
Shoichiro ASAYAMA
Associate Professor / Dr. Eng.
Biomaterials, Drug Delivery System, Biomedical Polymers,
Biomolecular Engineering, Biochemistry
Rm. 9-651, +81-42-677-1111 Ext. 4976
Master’s course -5
Bachelor 4 -3
■Outlines of the Research
To improve human health and quality of life (QOL), we have
designed new biomaterials. Especially, we have designed new
drug delivery system (DDS) for advanced and homogeneous
medicine as follows:
1. Nucleic Acid (Plasmid DNA, various RNAs) Delivery
System
Shoichiro ASAYAMA
As water-soluble (liquid-phase) biomaterials, the carriers of
nucleic acid as a macromolecular drug have been designed for
unmet medical needs. Recently, the mono-ion complex (MIC)
to make plasmid DNA (pDNA), as a gene, highly condensed has
been formed for delivery to in vivo unexplored space (Figure 1).
Figure 1. Delivery to in vivo unexplored space by the mono-
ion complex (MIC).
In this year, mono-cationic PEGs with an amide or ester
spacer between a terminal cation and PEG have been synthesized.
Furthermore, a di-cationic PEG with an ester spacer has been
synthesized. The mono-ion complex (MIC) and di-ion
complex (DIC) of plasmid DNA (pDNA) with the resulting
PEGs have been formed. The structure-activity relationship of
in vivo gene delivery by use of the MIC and DIC have been
demonstrated.
2. Bioactive Substance (Zn2+, protein) Delivery System
Shoichiro ASAYAMA
To give DDS carrier the ability for definitive treatment, we
have designed pH-sensitive polyvinylimidazole (PVIm)
derivateives as intelligent materials to change their structure and
function in respons to external stimuli. Recently, Zn2+ delivery
to liver is applied for remote control of hypoglycemic hormone
(Figure 2).
Figure 2. Remote control of hypoglycemic hormone in blood.
In this year, the zinc porphyrin-carbohydrate conjugate (ZnP-
Lac) has been synthesized for cellspecific delivery of Zn2+ ions.
The resulting ZnP-Lac without cytotoxicity was added to HepG2
cells as a human liver model. The intracellular uptake of Zn2+
treated with ZnP-Lac was higher than that with ZnCl2 alone.
These results suggest that the ZnP-Lac delivered Zn2+ by the
recognition of lactose with an asialoglycoprotein receptor
(ASGP-R) on the HepG2 cell.
3. Biomaterials with Funtional Surface
Shoichiro ASAYAMA
As water-insoluble (splid-phase) biomaterials, to design
medical devices working in vivo or ex vivo with efficient
biocompatibility, we have recently applied cholesterol end-
modified poly(ethylene glycol), that is, Chol-PEG, as DDS
carrier to the non-covalent modification of solid surface (Figure
3).
Figure 3. Development of novel bio-function by Chol-PEG.
In this year, the modification density of cholesterol end-
modified PEG (Chol-PEG) to poly(propylene) (PP) surface, and
the molecular weight dependence of Chol-PEG-modified PP
surface on the adsorption of biomolecules and blood constituent
cells were examined. As a result, the design of the bio-inert
surface with Chol-PEG with molecular weight of 2,000 has been
succeeded. The resulting bio-inert surface is expected to be
applied for in vivo implanted devices.
Delivery to Unexplored Space
Disease
NN
C(CH2)n
O
H2N PEG
+
+
+
+ Mono-Ion Complex【MIC】
Pancreas
Zn2+
Liver
Insulin
Insulin
secretion
Survival insulin
to whole body
Protein
CH
CH2
N
N
xCH
CH2
N
N
1-x-yCH
CH2
N
N
y
+
(CH2)nCH3Zn2+
OCH3O CH2CH2O CH2CH2CH2Nn
C
H
O
H3C
CH3
H3C
CH3
H3C
Most S im p le
Non cova len t
PEGyla t ion
By-product by conventional
covalent PEGylation
7 8 9 10 11 12
Elution volume / mL
Insulin
Surface modification
with biocompatibility
9
■Papers with Peer Review
1. Yuki Kobayashi, Sakura Taneichi, Hiroyoshi Kawakami,
Yoichi Negishi, Shoichiro Asayama, Plasmid DNA mono-ion
complex for in vivo sustainable gene expression, ACS Omega, 4,
11464-11471 (2019).
2. Riku Kubota, Shoichiro Asayama, Hiroyoshi Kawakami,
Catalytic antioxidants for Therapeutic Medicine, Journal of
Materials Chemistry B, 7, 3165-3191 (2019).
3. Akito Endo, Shoichiro Asayama, Preparation of Zn2+-chelated
carboxymethyl poly(1-vinylimidazole) for intracellular Zn2+
delivery, Journal of Minerals and Materials Characteriza-tion
and Engineering, 7, 213-220 (2019).
4. Kosuke Chikuma, Kohe Arima, Yutaro Asaba, Riku Kubota,
Shoichiro Asayama, Kiyoshi Sato, Hiroyoshi Kawakami, The
potential of lipid-polymer nanoparticles as epigenetic and ROS
control approaches for COPD, Free Radical Research, in press
(2019).
5. Shoichiro Asayama, Molecular design of polymer-based
carriers for plasmid DNA delivery in vitro and in vivo (Highlight
Review). Chemistry Letters, 49, 1-9 (2020).
6. Akito Endo, Taiga Nagakura, Hiroyoshi Kawakami, Shoichiro
Asayama, Synthesis and characterization of lactosylated poly(1-
vinylimidazole) for cell-specific plasmid DNA carrier, Internal
Medicine and Care, 4, 1-5 (2020).
■Academic Meeting
See the annual report in Japanese (13 articles)
10
Reports from Research Groups
Kubo Laboratory
■Members
Yuji Kubo
Professor /Dr. Eng.
Organic Chemistry, Supramolecular Chemistry, Functional Dye
Room: 9-539 TEL: +81-42-677-3134
e-mail: [email protected]
J. Yan Mulyana
Associate Professor / Ph.D. Coordination Chemistry, Photochemistry
Room: 9-149 TEL: +81-42-677-2823
e-mail: [email protected]
Ryuhei Nishiyabu
Assistant Professor / Dr. Eng. Supramolecular Chemistry, Organic Chemistry, Matetials
Chemistry
Room: 9-438 TEL: +81-42-677-1111 (Ext. 4941)
e-mail: [email protected]
Doctor’s course -3
Master’s course -11
Bachelor 4 -8
■Outlines of the Research
1. Synthesis of dye-sensitized photocatalysts for Hydrogen
Production by Water Splitting
Yuji Kubo
Abstract
A visible-to-near-infrared (visible-to-NIR) light-driven
photocatalyst was prepared by loading a boron-dipyrromethene
(BODIPY)-phenothiazine conjugate dye as a photosensitizer on
hierarchical porous TiO2 semiconductor. The loaded dye
showed panchromatic sensitization of the porous TiO2 and the
system exhibited hydrogen generation. This study provides
important information for the development of metal-free
organic photosensitizers with a wide spectral response up to the
NIR region for photocatalytic water-splitting hydrogen
production.
Figure 1. Dye-sensitized photocatalytic hydrogen production
by water splitting.
2. Synthesis of photosensitizers for application in
dye-sensitized solar cells
Yuji Kubo
This study has been collaborated with Prof. Dr. Şule
ERTEN-ELA (Solar Energy Institute, Ege University).
Abstract
Much attention has been devoted to the synthesis of dyes
that absorb near-infrared (NIR) radiation because of numerous
demands for them as functional materials. In this work, we
have tried to propose NIR absorbing photosensitizers
applicable to dye-sensitized solar cell (DSSC) devices.
Figure 2. Chemical structure of a sensitizer for application in
p-typed DSSC and EQE spectrum the dye-loaded p-type DSSC.
3. Synthesis of selenium-containing dyes as photosensitizers
for triplet–triplet annihilation upconversion
Yuji Kubo
Abstract
A series of selenium-containing BODIPY dyes were
synthesized as photosensitizers for triplet–triplet annihilation
upconversion (TTA-UC). The bis(phenylselanyl)-BODIPY
dyes with different substituents at the phenylselanyl groups
absorbed visible light and exhibited fluorescence with a low
fluorescence quantum yield. The low value was ascribed to
heavy atom effects. When TTA-UC systems comprising these
dyes as triplet donors and pelyrene as a triplet acceptor
perylene were set up, substituent-dependent TTA-UC behaviors
were observed.
Figure 3. Selenium-containing BODIPYs as sensitizers for
triplet–triplet annihilation upconversion.
4. Synthesis of Near Infrared (NIR) Light Absorbing Dye for
Photodetectors
Yuji Kubo
Abstract
A series of thieno[1,3,2]oxazaborinine-containing
aza-BODIPYs (1–3) were newly prepared as near infrared NIR
absorbing dyes. As a potential device application, the 3-loaded
film was prepared on indium tin oxide (ITO). The film showed
a NIR absorption band at 827 nm with a wide spectral range. Its
applicability as a NIR photodetector was evaluated through
fabrication of a single-component device. The ITO/3 (85
nm)/Al (100 nm) device produced a photocurrent of 9.57 × 10−7
A cm−2 at a bias potential of 1 V upon illumination at 850 nm
and a fluence of 130 μW cm−2.
Figure 4. Chemical structures of thieno[1,3,2]oxazaborinine
-containing aza-BODIPYs (1–3) and J–V curves of a 3-loaded
device (ITO/3 (85 nm)/Al (100 nm)) measured in the dark
(blue) and under illumination (red) at 850 nm (130 μW cm−2).
5. Room-temperature phosphorescence-active boronate
particles as ratiometric afterglow sensors
11
Reports from Research Groups
Yuji Kubo and Ryuhei Nishiyabu
Abstract:
We found that boronate particles (BP), as a self-assembled
system prepared by sequential dehydration of
benzene-1,4-diboronic acid with pentaerythritol, showed
greenish room-temperature phosphorescence. This emission
was observed in both solid and dispersion state in water and
ratiometric afterglow sensing of water content in an organic
solvent was achieved by grafting of a rhodamine onto the
surface of BP.
Figure 5. Ratiometric afterglow sensing of water content in an
organic solvent by room-temperature phosphorescence-active
boronate particles (BP).
6. Synthesis of nanostructured BiVO4/TiO2 modified with dye
and co-catalyst molecules for photo-induced water oxidation
Mulyana J. Yan
Abstract
The titanium oxide (TiO2)-coated bismuth vanadate
(BiVO4) photoanode surface-modified with a ruthenium
complex (Rutbipy dye) and a porphyrin copper complex
(CuTCPP) co-catalyst features a cascade hole transfer from
BiVO4 to the dye and to the co-catalyst molecule, which
improves the PEC performance.
Figure 6. The structure of the TiO2-coated BiVO4 photoanode
surface-modified with Rutbipy dye and CuTCPP co-catalyst.
7. Boronate sol–gel method for one-step fabrication of
polyvinyl alcohol hydrogel coatings by simple cast- and
dip-coating techniques
Ryuhei Nishiyabu and Yuji Kubo
Abstract
The self-assembly of polyvinyl alcohol (PVA) and
benzene-1,4-diboronic acid (DBA) is employed as a sol–gel
method for one-step fabrication of hydrogel coatings with
versatile functionalities. A mixture of PVA and DBA in aqueous
ethanol is prepared as a coating agent. The long pot life of the
mixture allows for the coating of a wide range of materials with
hydrogel films by simple cast- and dip-coating techniques.
Figure 7. Boronate sol–gel method for one-step fabrication of
polyvinyl alcohol hydrogel coatings by a simple dip-coating
technique.
8. Accurate chiral pattern recognition for amines from just a
single chemosensor
Yuji Kubo
This study was collaborated with Tsuyoshi Minami (Institute of
Industrial Science, The University of Tokyo).
Abstract
The current work proposes a novel determination method
for enantiomeric excess (ee) in (mono- and di-) amines using
molecular self-assembly. A pyridine-attached binaphthyl
derivative ((R)-1) exhibits fluorescence responses based on
imine formation between the aldehyde group of (R)-1 and
target chiral amines (i.e. cyclohexane diamine (CHDA),
2-amino-1,2-diphenylethanol (ADPE),
1,2-diphenylethylenediamine (DPDA), 1-amino-2-indanol
(AID), and leucinol in the presence of zinc(II) ions (Zn2+).
Because of the multi-optical responses which are derived from
the variation of chiral complexes, pattern recognition-based
discrimination (i.e. linear discriminant analysis (LDA)) has
been achieved for five types of enantiomeric pairs of amines.
Possessing such a discrimination capability in combination
with data processing (LDA and an artificial neural network)
allows accurate determination (prediction error < 1.8%) of
the % ee of individual targets such as CHDA which is one of
the main components of pharmaceutical drugs. The simple
molecular self-assembled system enabled simultaneous
multi-chiral discrimination and % ee determination of unknown
samples.
Figure 8. Enantioselective response for optically ative
diamines by self-assembled chiral chemosensors.
■Papers with Peer Review
1. Y. Sasaki, S. Kojima, V. Hamedpour, R. Kubota, S.
Takizawa, I. Yoshikawa, H. Houjou, Y. Kubo and T. Minami,
Accurate chiral pattern recognition for amines, albeit a
single chemosensor. Chem. Sci., 2020, accepted. DOI:
10.1039/D0SC00194E
2. M. Hoshi, R. Nishiyabu, Y. Hayashi, S. Yagi and Y. Kubo,
Room-temperature phosphorescence-active boronate
particles: characterization and ratiometric afterglow-sensing
behavior via surface grafting of Rhodamine B. Chem. Asian
J., 2020, accepted. DOI: 10.1002/asia.201901740
3. R. Nishiyabu, Y. Takahashi, T. Yabuki, S. Gommori, Y.
Yamamoto, H. Kitagishi and Y. Kubo, Boronate sol–gel
method for one-step fabrication of polyvinyl alcohol
hydrogel coatings by simple cast- and dip-coating
techniques. RSC Adv., 2020, 20, 86‒94. DOI:
10.1039/C9RA08208E
12
Reports from Research Groups
4 Y. Kubo, T. Shimada, K. Maeda
and Y. Hashimoto,
Thieno[1,3,2]oxazaborinine-con
taining aza-BODIPYs with near
infrared absorption bands:
synthesis, photophysical
properties, and device
application. New J. Chem., 2020,
44, 29-37. DOI:
10.1039/C9NJ04612G
5. Y. Higashino, S. Erten-Ela and
Y. Kubo, π-Expanded dibenzo-BODIPY with near-infrared
light absorption: investigation of photosensitizing properties
of NiO-based p-type dye-sensitized solar cells. Dyes and
Pigments, 2019, 170, 107613. DOI:
10.1016/j.dyepig.2019.107613
6. U. Pratomo, I. Purnama and Y. J. Mulyana, Photo-induced
water oxidation via cascade charge transfer on
nanostructured BiVO4/TiO2 modified with dye and
co-catalyst molecules, Inorg. Chim. Acta, 2020, 500,
119223. DOI: 10.1016/j.ica.2019.119223
7. O. Suryani, Y. Higashino, H. Sato and Y. Kubo,
Visible-to-near-infrared light-driven photocatalytic
hydrogen production using dibenzo-BODIPY and
phenothiazine conjugate as organic photosensitizer. ACS
Appl. Energy Mater., 2019, 2, 448‒458. DOI:
10.1021/acsaem.8b01474
■Invited Lectures
1. Near-infrared absorbing dibenzo-BODIPYs; Synthesis,
properties, and applications, Yuji Kubo, Lecture at Ege
University (Izmir, Turkey), July 22, 2019.
2. Solid-State Emissive Chemosensors based on Boronate
Supramolecules, Yuji Kubo, 3rd Asian Conference on
Chemosensors and Imaging Probes" (Asian-ChIP 2019),
Amritsar, India, November 7, 2019.
3. Preparation of solid catalysis and solid-based
luminescence materials based on boronate supramolecules,
Yuji Kubo, 19-2 Research group on supramolecules (The
Society of Polymer Science), Tokyo, January 24, 2020 (in
Japanese).
4. Synthesis of visible light and near-infrared absorbing dyes
for efficient light-induced hydrogen production, Yuji Kubo,
4S8-09 (Special Program lecture), The 100th CSJ Annual
meeting, March 25, 2020 (in Japanese).
■Academic Meeting
See the annual report in Japanese (17 articles)
13
Reports from Research Groups
Setaka Laboratory
■Members Wataru Setaka Professor /Dr. Sci. Physical Organic Chemistry, Functional Organic Chemistry room: 9-542 TEL: +81-42-677-1111 (Ext.4955) e-mail: [email protected] Yusuke Inagaki Assistant Professor / Dr. Sci. Main-group Chemistry, Functional Organic Chemistry room: 9-545 TEL: +81-42-677-1111 (Ext.4957) e-mail: [email protected] Doctor’s course -0 Master’s course -5 Bachelor 4 -5
■Outlines of the Research Development of Highly Designed Organic Molecules Wataru SETAKA, and Yusuke INAGAKI Development of organic molecules of which strucrure and functions are highly designed would improve our daily life with respect to energy saving and environmental consequence. Our interest lies in the design and synthesis of organic molecules with new structures that incorporate silicon to develop molecules with new functions. Specifically, we are studying the relationship between molecular structure and molecular functionalities of novel organosilicon compounds. 1. Crystalline Molecular Gyrotop A molecular machine has been defined as a discrete number of molecular components that perform mechanical─like movements in response to specific stimuli. A macrocage molecule with a bridged thiophene rotor was synthesized as a molecular gyrotop having a dipolar rotor, given that the dipole derived from the thiophene can rotate even in the crystal. The thermally induced change in the orientation of the dipolar rotors (thiophene ring) inside the crystal, i.e., order-disorder transition, and the variation in the optical properties in the crystalline state were observed.
Figure 1. molecular gyrotop. We have reported our rewiews regarding chemistry of molecular gyrotops (Review #1). In this year, following papers were published. Methylcarbazole is known as efficient fluorophore. In this study, methylcarbazole bridged macrocage was designed and synthesized. Unfortunately, the carbazole moiety shows no rotation in a crystalline state. However, highly polarized fluorescence was observed due to unidirectional alignment of the carbazolue in a crystalline state (Figure 2, paper #4).
Figure 2. Structure and Polarized fluorescence of the crystal of methylcarbazole bidged macrocage (paper #4). Carbazole nitroxide is known as labile radical species due to extended pi-electron systems. We designed carbazole nitroxide bridged macrocage as kinetically stabilized mitroxide. Actually the life time of the radical was investigated by ESR spectroscopy. Remarkablly long life-time of the radical were observed (Figure 3, paper #2).
Figure 3. Structure and ESR spectrum of carbazole nitroxide bridged macrocage (paper #2). 2. Novel Molecular Bevel Gears Ditriptycilmethanes are known as molecular bevel gears because the two triptycil groups show correlated rotation. In this report, molecular bevel gears bridged with a group 14 element, bis(methyltriptycil)X (X = SiH2, GeH2, GeF2), were synthesized, and their gearing properties were investigated. Gear slippage, that is an error in gear rotation, is observed in high-temperature solutions of molecular bevel gears. Heavy atom derivatives undergo gear slippage more easily due to the long bond lengths and wide angles between the two triptycil units and the bridging group 14 element. Activation energies of gear slippages were estimated by temperature-dependent NMR spectroscopy and DFT calculations, and theoretical thermodynamic parameters for gear slippage were found to be in excellent agreement with experimental values. The results indicate that theoretical calculations for gear rotation in molecular bevel gears can accurately reproduce experimental phenomena. (Figure 4, paper #2).
Figure4. Gear slippage in a germanium-bridged molecular gears.
14
Reports from Research Groups
Construction of hydrogen-bonded networks among hydroxyl groups has often been utilized to synthesize specific structures on the basis of supramolecular chemistry. In this study, resorcyltriptycene was designed as a possible component of a crystalline molecular gear, because the molecule has a triptycyl wheel and a resorcyl linker which can be involved in intermolecular alignments in a crystal, as mediated by hydrogen-bonded networks. The synthesis and crystal structure of resorcyltriptycene are reported here. The gear alignment among triptycyls in a crystalline state was achieved in a crystal structure of resorcyltriptycene containing water in the intermolecular spaces. However, rotations of triptycyls in the crystalline state was suppressed by steric interaction with the water molecules. This crystal structure was stabilized by O–HꞏꞏꞏCπ(phenyl) interactions between triptycyl and the hydrated water. Moreover, single crystals without solvent and with methanol were obtained from a dry toluene solution and a methanol solution, respectively. Transformations among the single crystals were observed by heating or drying or soaking in a solvent. It is significant that various crystal structures dependent on the condition were observed. The observed phenomena should aid the design of functional crystals. (Figure 5, paper #1).
Figure 5. Crystal structure of resolcyltriptycene hydrate.
■Papers with Peer Review 1. Gear Alignments due to Hydrogen-Bonded Networks in a
Crystal Structure of Resorcyltriptycene Hydrate and its Transformation to a non-Gearing Anhydrate Crystal by Heating, N. Tanaka, Y. Inagaki, K. Yamaguchi, and W. Setaka, Cryst. Growth Des., 20(2), 1097-1102 (2020). DOI:10.1021/acs.cgd.9b01424
2. Gear Slippage in Molecular Bevel Gears Bridged with a
Group 14 Element, K. Okamura, Y. Inagaki, H. Momma, E. Kwon, and W. Setaka, J. Org. Chem., 84(18), 14636-14643 (2019). DOI:10.1021/acs.joc.9b02214
3. Kinetic Stabilization of Carbazole Nitroxides by Inclusion
in a Macrocage and their ESR Characterization, H. Hashimoto, Y. Inagaki, H. Mommma, E. Kwon, and W. Setaka, J. Org. Chem., 84(18), 11783-11789 (2019). DOI:10.1021/acs.joc.9b01686
4. Polarized Fluorescence of a Crystal having Uniaxially
Oriented Molecules by a Carbazole-diyl-bridged Macrocage, H. Hashimoto, Y. Inagaki, H. Momma, E. Kwon, K. Yamaguchi, and W. Setaka, CrystEngComm, 21, 3910-3914 (2019). DOI: 10.1039/C9CE00706G
■Review 1. Chemistry of Macrocage Molecules with a Bridged
pi-Electron System as Crystalline Molecular Gyrotops, Wataru Setaka, Yusuke Inagaki, and Kentaro Yamaguchi, J. Synth. Org. Chem., J., 77(8), 813-822 (2019). DOI: 10.5059/yukigoseikyokaishi.77.813
■Invited Lecture 1. Chemistry of Molecular Gyrotops
W. Setaka Molecular Rotor Workshop 2019 , 2019.11.21-22, the Institute of Organic Chemistry and Biochemistry of the CAS(Prague, Czech Republic)(invited)
■Awards 1. Daiki Hayash, 46th onferenceof Main Group Element
Chemistry, ChemCommPresentationPrize、2019.12.. ■Academic Meeting *International 1. Facile Synthesis of Tetrasilyl[2]acediyne
Kazuki Komatsubara, Yusuke Inagaki, Wataru Setaka The 4th International Symposium on Hydrogen Energy-based Society, 2019.8.22-23, Tokyo Metropolitan University(Tokyo, Japan) (8/22, P-22) (poster)
2. Thiophene-Dioxide Bridged Macrocages as Crystalline
Fluorescent Molecular Gyrotops Wataru Setaka, Daiki Hayashi, Miyako Tsurunaga, Yusuke Inagaki, and Kentaro Yamaguchi 18th International Symposium on Novel Aromatic Compounds (ISNA-18), Sapporo Convention Center, 2019.7.21-26, (Sapporo, Japan)(7/22, 317) (poster)
*Domestic 1. Synthesis and Crystal Structures of Isophthalyltriptycene
Syuuto Ohyama, Yusuke Inagaki, Wataru Setaka The 100th CSJ Annual Meeting, Noda Campus, Tokyo University of Science, 2020.3.22-25. (Chiba, Japan).(3/25 4B7-34)(oral)
2. Synthesis of Acediynes by Utilizing Bulkiness of Silyl
Groups Kazuki Komatsubara, Yusuke Inagaki, Wataru Setaka The 100th CSJ Annual Meeting, Noda Campus, Tokyo University of Science, 2020.3.22-25. (Chiba, Japan).(3/22 1C4-37)(oral)
3. Synthesis and Fluorescence Properties of Silyl-substituted
Benzo[b]thiophene-1,1-dioxides Keita Nobuhara, Yusuke Inagaki, Wataru Setaka The 100th CSJ Annual Meeting, Noda Campus, Tokyo University of Science, 2020.3.22-25. (Chiba, Japan).(3/22 1B7-43)(oral)
4. Relation between Solid-state Fluorescence Intensity and
Motion of a Fluorophore in Thienothiophene-dioxide Bridged Molecular Gyrotops Daiki Hayashi, Yusuke Inagaki, Wataru Setaka 46th Main Group Element Chemistry , Matsuyama University, 2019.12.5-7 (Ehime, Japan). (12/5 O-21)(oral)
5. Facile Synthesis of Tetrasilyl[2]acediyne due to bulky silyl
groups Kazuki Komatsubara, Yusuke Inagaki, Wataru Setaka 9th CSJ Chemistry Festa, Tower Hall of Fenabori, 2019.10.15-17 (Tokyo, Japan).(10/16 P4-029)(poster)
15
Reports from Research Groups
Kanamura Laboratory
■Members
Kiyoshi KANAMURA
Professor /Dr. Eng.
Inorganic Industrial Chemistry, Energy Chemistry,
Electrochemistry
room:9-247 TEL: +81-42-677-2828
e-mail: [email protected]
Hirokazu MUNAKATA
Assistant Professor /Ph.D.
Electrochemistry, Inorganic Material Chemistry,
Batteries and Fuel Cells
room:9-246 TEL: +81-42-677-2826
e-mail: [email protected]
Doctor’s course -3
Master’s course -13
Bachelor 4 -7
■Outlines of the Research
1. Research on rechargeable magnesium batteries
Kiyoshi KANAMURA
Rechargeable magnesium batteries are attracting much attention
as next generation batteries to replace current lithium ion
batteries due to its abundant resources on the earth. In this FY,
we made and evaluated rechargeable magnesium batteries with
practical laminated-forms in addition to the exploration of new
materials to improve the batteriy performance.
Fig. 1 The charge and discharge curves of a rechargeable
magnesium battery with a practical laminated-form (cathode:
NiCo2O4, anode: Mg alloy).
2. Research on safe and high capacity rechargeable lithium
batteries
Kiyoshi KANAMURA, Hirokazu MUNAKATA
The development of rechargeable lithium batteries with lithium-
metal anode was carrired out in order to realize high energy
density. Lithium-metal anode has about ten times larger
gravimetric capacity than currently-used graphite anode.
However, its practical use requires the improvement of cycle
performance in addition to the suppression of needle-like
deposition of lithium metal. In this FY, we focused on the effects
of kind and concentration of Li salt in electrolyte solutions on
the cycle performance of lithium-metal anode (Fig. 2) and also
the formation of artificial ion conducting layers for smooth
deposition/dissolution of lithium-metal (Fig. 3). The
development of flexible quasi-solid electrolyte membranes
including Li+-ion conducting ceramic electrolyte is also
continuously performed as in the previous FY as another
approach to improve the safety of rechargeable lithium-metal
batteries.
Fig.2 Comparison of coulombic efficiencies of lithium-metal
anode in 1 mol dm-3 LiPF6 / EC and 4.5 mol dm-3 LiFSI / EC.
Fig.3 Improvement of deposition flatness of lithium metal by
the formation of an artificial ion-conducting layer.
3. Research on fuel cells
Kiyoshi KANAMURA, Hirokazu MUNAKATA
Toward the realization of a hydrogen society, the development
of a new fuel cell system that works at intermediate temperatures
over 100 °C under non-humidified conditions was promoted
continuously in this FY based on the use of phosphoric acid /
ionic liquid mixed electrolytes that have high proton
conductivity and thermal stability. As increasing the operating
temperature, the energy conversion efficiency of fuel cells can
be increased but the dissolution of platinum catalysts also is
enhanced. In this FY, we focused on the dissolution behavior of
platinum catalysts and found that high durability can be achieved
for platinum catalysts in the phosphoric acid / ionic liquid mixed
electrolytes (Fig. 4). For the reduction of fuel cell cost, non-
platinum carbon-based catalysts were also studied.
Fig. 4 Transmission electronic microscope images of platinum
catalysts before (upper image) and after the durability test in
phosphoric acid (lower-left image) and in the phosphoric acid /
ionic liquid mixed electrolyte (lower-right image).
1 mol dm-3
LiPF6 / EC4.5 mol dm-3
LiFSI / EC
16
Reports from Research Groups
■Papers with Peer Review
1. Koki Nakano, Yusuke Noda, Naoto Tanibata, Masanobu
Nakayama, Koichi Kajihara, Kiyoshi Kanamura,
Computational investigation of the Mg-ion conductivity
and phase stability of MgZr4(PO4)6, RSC Adv., 9,12590-
12595 (2019).
2. Yuto Shimizu, Kiyoshi Kanamura, Three Dimensionally
Ordered Macroporous Polybenzimidazole Separator for
Li Metal Battery, Chem. Lett., 48, 429–432 (2019).
3. Kohei Shimokawa, Taruto Atsumi, Maho Harada, Robyn
E. Ward, Masanobu Nakayama, Yu Kumagai, Fumiyasu
Oba, Norihiko L. Okamoto, Kiyoshi Kanamura, Tetsu
Ichitsubo, Zinc-based spinel cathode materials for
magnesium rechargeable batteries: toward the reversible
spinel–rocksalt transition, J. Mater. Chem. A, 7, 12225-
12235 (2019).
4. Motoko Nagasaki, Kiyoshi Kanamura, High-Performance
Lithium Metal Rechargeable Battery Using an Ultrafine
Porous Polyimide Separator with Three-Dimensionally
Ordered Macroporous Structure, ACS Applied Energy
Materials, 2, 3896-3903 (2019).
5. Jihun Song, Williams Agyei Appiah, Kim Sung-Soo,
Hirokazu Munakata, Kiyoshi Kanamura, Myung-Hyun
Ryou, Yong Min Lee, 3D electrochemical model for a
Single Secondary Particle and its application for
operando analysis, Nano Energy, 62, 810-817 (2019).
6. Toshihiko Mandai, Kenji Tatesaka, Kenya Soh, Hyuma
Masu, Ashu Choudhary, Yoshitaka Tateyama, Ryuta Ise,
Hiroaki Imai, Tatsuya Takeguchi, Kiyoshi Kanamura,
Modifications in coordination structure of Mg[TFSA]2-
based supporting salts for high-voltage magnesium
rechargeable batteries, Physical Chemistry Chemical
Physics, 21, 12100-12111 (2019).
7. Yuta Maeyoshi, Dong Ding, Masaaki Kubota, Hiroshi Ueda,
Koji Abe, Kiyoshi Kanamura, Hidetoshi Abe, Long-Term
Stable Lithium Metal Anode in Highly Concentrated
Sulfolane-Based Electrolytes with Ultrafine Porous
Polyimide Separator, ACS Appl. Mater. Interfaces, 11,
25833-25843 (2019).
8. Yong Zhang, Masashi Konya, Ayaka Kutsuma,
Seonghyeon Lim, Toshihiko Mandai, Hirokazu Munakata,
Kiyoshi Kanamura, Magnesium Storage Performance and
Mechanism of 2D ‐ Ultrathin Nanosheet ‐ Assembled
Spinel MgIn2S4 Cathode for High ‐ Temperature Mg
Batteries, Nano Micro Small, 15, 1902236 (2019).
9. Motoko Nagasaki, Kei Nishikawa, Kiyoshi Kanamura,
Deterioration Analysis of Lithium Metal Anode in Full
Cell during Long-Term Cycles, J. Electrochem. Soc., 166,
A2618-A2628 (2019).
10. Nurzhan Umirov, Yuto Yamada, Hirokazu Munakata,
Sung-Soo Kim, Kiyoshi Kanamura, Analysis of intrinsic
properties of Li4Ti5O12 using single-particle technique, J.
Electroanal. Chem., 855, 113514 (2019).
11. Seonghyeon LIM, Hirokazu MUNAKATA, Kiyoshi
KANAMURA, Carbon Coating for Improvements of
Electrochemical Properties of Li1.1V0.9O2 Anode Active
Materials for Li Secondary Batteries, Electrochemistry,
88, 22-27 (2020).
12. Eric Jianfeng Cheng, Takeshi Kimura, Mao Shoji, Hiroshi
Ueda, Hirokazu Munakata, Kiyoshi Kanamura, Ceramic-
Based Flexible Sheet Electrolyte for Li Batteries, ACS
Appl. Mater. Interfaces, doi.org/10.1021/acsami.9b21251
(2020).
■Books and reviews
See the annual report in Japanese (8 articles)
■Invited Lectures
*International
1. Kiyoshi Kanamura, Lithium Metal Electrode 3D Separator,
LBIS 2019 4th Lithium Battery International Summit,
2019年5月, Hyatt Regency Shenzhen Airport, Shenzhen,
China.
2. Kiyoshi Kanamura, All Solid State Battery Prepared by
Composite Type Solid Electrolyte, INESS 2019 The 7th
International Conference on Nanomaterials and
Advanced Energy Storage Systems, 2019 年 8 月, Al-
Farabi Kazakh National university, Almaty, Kazakhstan.
3. H. Munakata, H. Inoue, T. Kimura, E.J. Cheng, K. Kanamura,
Development of Flexible Composite Electrolyte Sheets
for Next-Generation Batteries, 2nd World Conference on
Solid Electrolytes for Advanced Applications: Garnets
and Competitors, 2019年9月, Granship, Shizuoka, Japan.
4. Kiyoshi Kanamura, Direct Fabrication of Cathode Layer
Onto Oxide-Based Solid Electrolyte with Good Interface,
236th ECS Meeting, 2019年 10月, Hilton Atlanta, Atlanta,
USA.
5. Hirokazu Munakata, Jungo Wakasugi, Kyoko Kozuka,
Katsuya Honmou, Mao Shoji, Takeshi Kimura and Kiyoshi
Kanamura, Cathode design for rechargeable lithium-metal
batteries with Li6.25Al0.25La3Zr2O12 solid electrolyte,
PACRIM13, 2019 年 10 月, Okinawa Convention Center,
Okinawa, Japan
6. Hirokazu Munakata, Yamato Nagahori, Kiyoshi Kanamura,
Electrochemical evaluation of electrode active materials
by using μ-cavity current collector, WSLIBNGB 2019
The 3rd Work Shop on Lithium Ion Battery and Next
Generation Batteries 2019, 2019 年 11 月, Chungnam
National University, Daejeon, Korea.
*Domestic
See the annual report in Japanese (3 articles including 1
requested lecture)
■Academic Meeting
*International
1. Dong Ding, Yuta Maeyoshi, Masaaki Kubota, Jungo
Wakasugi, Kiyoshi Kanamura, Hidetoshi Abe, A Facile Way
to Synthesize Carbon-Coated LiMn0.7Fe0.3PO4/Reduced
Graphene Oxide Sandwich-Structured Composite for
Lithium Ion Batteries, 235th ECS Meeting, 2019 年 5 月,
Sheraton Dallas, Dallas, USA.
2. Feilure Tuerxun, Masashi Hattori, Kentaro Yamamoto,
Toshihiko Mandai, Masaki Matsui, Yoshitaka Tateyama,
Tomoki Uchiyama, Tatsuya Takeguchi, Kiyoshi Kanamura,
Yoshiharu Uchimoto, Interfacial Behavior of Magnesium
Ions at Electrode/Electrolyte Interface during Magnesium
Deposition Reaction, 235th ECS Meeting, 2019 年 5 月,
Sheraton Dallas, Dallas, USA.
3. Yuta Maeyoshi, Masaaki Kubota, Hidetoshi Abe, Koji Abe,
Kiyoshi Kanamura, Effect of Salt Concentration in
Sulfolane-Based Electrolyte on Long-Term Li
17
Reports from Research Groups
Plating/Stripping Behavior, 235th ECS Meeting, 2019 年
5 月, Sheraton Dallas, Dallas, USA.
4. Jie. Yu, H. Miura, H. Munakata, T. Shishido, K. Kanamura,
Development of membrane electrode assembly applying
on methanol-reforming-hydrogen/ oxygen intermediate
temperature fuel cell system, The World Hydrogen
Technologies Convention 2019, 2019 年 6 月 , Tokyo
International Forum, Tokyo, Japan.
5. K. Kanamura, M. Shoji, E. Cheng, Development of Flexible
Composite Solid Electrolyte and Quasi-solid Composite
Cathode for Practical Realization of Solid-state Lithium-
ion Batteries, GFMAT-2, 2019 年 7 月, Toronto Marriott
Downtown at CF Eaton Centre Hotel, Toronto, Canada.
6. Yong Zhang, Eric Jianfeng Cheng, Yuto Yamada, Yukihiro
Nakabayashi, Mao shoji, Jin Niu, Jae-sang Park, Hirokazu
Munakata, Kiyoshi Kanamura, Innovative Next Generation
Batteries for Low Carbon Society, The 4th International
Symposium on Hydrogen Energy-based Society, 2019 年
8 月, Tokyo Metropolitan University, Tokyo, Japan.
7. Jie. Yu, H. Miura, H. Munakata, T. Shishido, K. Kanamura,
Development of non-humidified intermediate
temperature methanol-reforming-hydrogen/ oxygen fuel
cell system, The 4th International Symposium on
Hydrogen Energy-based Society, 2019 年 8 月, Tokyo
Metropolitan University, Tokyo, Japan.
8. Koichi Kajihara, Mayu Suda, Ryosui Nakagawa, Kiyoshi
Kanamura, Highly-transparent efficient sol–gel-derived
silica – (Gd,Pr)PO4 glass-ceramic narrow-band UVB
phosphors, Photoluminescence in Rare Earths 2019
(PRE19), 2019年9月, Hotel Aston La Scala, Nice, France.
9. E. Cheng, T. Kimura, M. Shoji, H. Munakata, K. Kanamura,
Flexible Al-Li7La3Zr2O12 Composite Sheet Electrolyte for
Li Metal Batteries, 2nd World Conference on Solid
Electrolytes for Advanced Applications: Garnets and
Competitors, 2019 年 9 月, Granship, Shizuoka, Japan.
10. K. Hommo, M. Shoji, H. Munakata, K. Kanamura, Interfacial
Formation between LiCoO2 and Li6.25Al0.25La3Zr2O12 using
Lithium-ion Conductive Liquid, 2nd World Conference on
Solid Electrolytes for Advanced Applications: Garnets
and Competitors, 2019年9月, Granship, Shizuoka, Japan.
11. Eric Jianfeng Cheng, Takeshi Kimura, Hirokazu Munakata,
Kiyoshi Kanamura, Garnet-Based Flexible Composite
Sheet Electrolyte, 236th ECS Meeting, 2019 年 10 月,
Hilton Atlanta, Atlanta, USA.
12. Jie Yu, Hirokazu Munakata, Kiyoshi Kanamura,
Development of 3-Dimensionally Ordered Microporous
Polyimide Based Composite Membranes Apply on Non-
Humidified Intermediate Temperature Fuel Cells, 236th
ECS Meeting, 2019 年 10 月, Hilton Atlanta, Atlanta, USA.
13. Tsutomu Hashimoto, Kiyoshi Kanamura, Life Prediction of
Lithium Ion Battery for Grid Scale Energy Storage
System, 236th ECS Meeting, 2019年10月, Hilton Atlanta,
Atlanta, USA.
14. Yuto Yamada, Takeshi Kimura, Yosuke Kushida, Mao Shoji,
Kiyoshi Kanamura, Electrochemical Analysis Using
Microelectrode for Cathode Materials Deposited on a
Solid Electrolyte Pellet By Using Aerosol Deposition
Method, 236th ECS Meeting, 2019年10月, Hilton Atlanta,
Atlanta, USA.
15. Koki NAKANO, Yusuke NODA, Naoto TANIBATA,
Masanobu NAKAYAMA, Koichi KAJIHARA, Kiyoshi
KANAMURA, Evaluation of the Mg-ion conductivity and
phase stability of Mg-ion conductor MgZr4(PO4)6 by DFT
method, PACRIM13, 2019 年 10 月, Okinawa Convention
Center, Okinawa, Japan.
16. Ryosuke SETO, Koichi KAJIHARA, Kiyoshi KANAMURA,
Cosolvent-free synthesis and characterization of
poly(Ph-co-R-SQ) (R = Me, Et, Pr, and Vi) glasses with
low melting temperatures, PACRIM13, 2019 年 10 月,
Okinawa Convention Center, Okinawa, Japan.
17. Koichi Kajihara, Ryosuke Seto, Kiyoshi Kanamura, Yohei
Onodera, Shinji Kohara, Microscopic ordering in
amorphous poly(n-alkylsilsesquioxane) liquids and solids
synthesized by a cosolvent-free hydrolytic
polycondensation via aging, PACRIM13, 2019 年 10 月,
Okinawa Convention Center, Okinawa, Japan.
18. Jae-sang, PARK, YOSUKE Kushida, KYOSHI Kanamura,
Effect of heat treatment on electrochemical properties
of interface between LiCoO2-Li3BO3 composite and
ceramic type solid electrolyte formed by aerosol
deposition method, PACRIM13, 2019 年 10 月, Okinawa
Convention Center, Okinawa, Japan.
19. Hiroki Yamashita, Jun Ikegami, Yuko Hirayama, Takaaki
Ogami, Yuto Yamada, Kiyoshi Kanamura, Synthesis and
electrochemical properties of LiMn1-xFexPO4/C
secondary particles, PACRIM13, 2019 年 10 月, Okinawa
Convention Center, Okinawa, Japan.
20. Koichi Kajihara, Ryosuke Seto, Kiyoshi Kanamura, Yohei
Onodera, Shinji Kohara, Microscopic ordering in
amorphous poly(n-alkylsilsesquioxane) liquids and solids
synthesized by a cosolvent-free hydrolytic
polycondensation via aging, PACRIM13, 2019 年 10 月,
Okinawa Convention Center, Okinawa, Japan.
21. Eric Jianfeng Cheng, Takeshi Kimura, Hirokazu Munakata,
Kiyoshi Kanamura, Ceramic-based Flexible Composite
Sheet Electrolyte for Li-metal Batteries, PACRIM13,
2019 年 10 月, Okinawa Convention Center, Okinawa,
Japan.
22. Yusuke Uetake, Shunsuke Asahina, Natasha Erdman,
Tamae Omoto, Hirokazu Munakata, Direct Analysis of
Lithium in LIB Cathode Using Soft X-Ray Emission
Spectrometer, 2019 MRS Fall Meeting & Exhibit, 2019 年
12 月, Hynes Convention Center, Boston, USA.
*Domestic
See the annual report in Japanese (31 articles)
18
Reports from Research Groups
Kajihara Laboratory
■Member Koichi KAJIHARA Associate Professor /Ph.D. Inorganic Chemistry, Functional Material Chemistry, Inorganic Materials/Physical Properties room:9-336 TEL: +81-42-677-2827 e-mail: [email protected] Master’s course -4 Bachelor 4 -3
■Outlines of the Research 1. Studies on silica-based materials Koichi KAJIHARA Silica is a ubiquitous material and its utilization is in accordance with SDGs. Silsesquioxanes (SQs) are silica-based organic-inorganic hybrids with a general formula RSiO3/2. We have developed cosolvent-free synthesis method of SQ polymers, an environmental-friendy synthesis method of SQ polymers, and are trying to utilize them. This FY we focused on poly(phenylsilsesquoxane)-based glasses with low melting temperatures. The cosolvent-free method provided a facile way to form these glasses with low melting temperatures. The resultant glasses exhibited several unique properties, including strong adhesion to glass plates as a result of the presence of many SiOH groups, and high fragility corresponding to a rapid viscosity decrease above the glass transition temperature. The brittleness of poly(phenylsilsesquioxane)s, which is well known for this type of glasses, was found to be suppressed by copolymerization with SQ units of aliphatic functional groups. These glasses are attractive as glasses with low melting temperatures. In addition, the presence of CH/ bondings, which probably works as cohesive forces, were confirmed.
Fig. 1 Poly(phenylsilsesquioxane) glasses melted at various temperatures (top), poly(phenyl-co-ethylsilsesquioxane) glasses melted on a glass plate (bottom left), and two glass plates bonded with this type of glass (bottom right). 2. Studies on battery-related materials Koichi KAJIHARA Abstract Studies of oxide-based battery-related materials were conducted. This FY we performed theoretical studies on Mg2+-ion-conducting oxide MgZr4(PO4)6. In corroboration with Nagoya Institute of Technology. Our group has succeded the high-temperature direct-current conductivity measurement of this compound using Mg metal electrodes. Ab-initio DFT calculations indicated that real MgZr4(PO4)6 crystals have monoclinic crystal structure, whereas its hexagonal polymorph with higher symmetry should have lower activation barriers for Mg2+ ion conduction and thus should exhibit higher Mg2+ ion conductivity.
Fig. 2 Schematic illustration of crystal structures and Mg2+-ion conduction paths derived by ab-initio theoretical calculations for Mg2+-ion-conducting ceramics MgZr4(PO4)6.
■Papers with Peer Review 1. K. Nakano, Y. Noda, N. Tanibata, M. Nakayama, K. Kajihara,
K. Kanamura, Computational investigation of the Mg-ion conductivity and phase stability of MgZr4(PO4)6, RSC Adv. 9, 12590-12595 (2019)
2. R. Seto, K. Kanamura, S. Yoshida, K. Kajihara, Cosolvent-free synthesis and characterisation of poly(phenyl-co-n-alkylsilsesquioxane) and poly(phenyl-co-vinylsilses-quioxane) glasses with low melting temperatures, Dalton Trans. 49, 2487-2495 (2020).
■Reviews *Domestic
See the annual report in Japanese (1 article)
■Academic Meeting *International 1. M. Saito, K. Kajihara, M. Shoji, Y. Kizuki, H. Munakata, K.
Kanamura, A solid-state lithium secondary battery using a chloroboracite-based glass-ceramic solid electrolyte, The 4th International Symposium on Hydrogen Energy-Based Society, Tokyo, Japan, 2019/8/22
2. L. Skuja, N. Ollier, K. Kajihara, K. Smits, Zero-phonon line and vibrionic structures in the green luminescence band in irradiated pure alpha-quartz, The 20th International conference on Radiation Effects in Insulators (REI-20), Astana, Kazakhstan, 2019/8/22
3. K. Kajihara, M. Suda, R. Nakagawa, K. Kajihara, Highly-transparent efficient sol–gel-derived silica–(Gd,Pr)PO4 glass-ceramic narrow-band UVB phosphors, The 8th International Workshop on Photoluminescence in Rare Earths: Photonic Materials and Devices (PRE19), Nice, France, 2019/9/6
4. L. Skuja, N. Ollier, K. Kajihara, Luminescence of non-bridging hole centers as a marker of particle irradiation of -quartz, The 19th International Conference on Solid State Dosimetry (SSD19), Hiroshima, Japan, 2019/9/17
5. R. Iwasaki, K. Kajihara, Photoluminescence of sol−gel-derived transparent silica−(Tb,Ce)PO4 glass-ceramics, The 13th Pacific Rim Conference of Ceramic Societies (PACRIM13), Okinawa, Japan, 2019/10/28
6. R. Nakagawa, K. Kajihara, Photoluminescence of sol−gel- derived transparent silica−(Gd,Pr)PO4 glass-ceramics under excitation with a KrCl excimer lamp, The 13th Pacific Rim Conference of Ceramic Societies (PACRIM13), Okinawa, Japan, 2019/10/28
7. R. Seto, K. Kajihara, K. Kanamura, Cosolvent-free synthesis and characterization of poly(Ph-co-R-SQ) (R = Me, Et, Pr, and Vi) glasses with low melting temperatures, The 13th Pacific Rim Conference of Ceramic Societies (PACRIM13), Okinawa, Japan, 2019/10/29
19
Reports from Research Groups
8. M. Saito, K. Kajihara, M. Shoji, Y. Kizuki, H. Munakata, K. Kanamura, Fabrication of a solid-state lithium secondary battery using a lithium-ion-conducting Li4B4Al3O12Cl-based glass-ceramic, The 13th Pacific Rim Conference of Ceramic Societies (PACRIM13), Okinawa, Japan, 2019/10/29
9. K. Nakano, Y. Noda, N. Tanibata, M. Nakayama, K. Kajihara, K. Kanamura, Evaluation of the Mg-ion conductivity and phase stability of Mg-ion conductor MgZr4(PO4)6 by DFT method, The 13th Pacific Rim Conference of Ceramic Societies (PACRIM13), Okinawa, Japan, 2019/10/29
10. K. Kajihara, R. Seto, K. Kanamura, Y. Onodera, S. Kohara, Microscopic ordering in amorphous poly(n- alkylsilsesquioxane) liquids and solids synthesized by a cosolvent-free hydrolytic polycondensation via aging, The 13th Pacific Rim Conference of Ceramic Societies (PACRIM13), Okinawa, Japan, 2019/10/30
*Domestic See the annual report in Japanese (5 articles)
■Patents *Domestic See the annual report in Japanese (1 article)
■Awards 1. M. Saito, Best Poster Award in Symposium 20: Ceramics for
Rechargeable Energy Storage at the 13th Pacific Rim Conference of Ceramic Societies (PACRIM13) M. Saito, K. Kajihara, M. Shoji, Y. Kizuki, H. Munakata, K. Kanamura, Fabrication of a solid-state lithium secondary battery using a lithium-ion-conducting Li4B4Al3O12Cl-based glass-ceramic
2. K. Kajihara, 2019 Leading Professor in Faculty of Urban Environmental Sciences, Tokyo Metropolitan University
20
Reports from Research Groups
Takagi Laboratory
■Members Shinsuke TAKAGI Professor /Ph.D Photochemistry, Photo-functional Materials Chemistry, Porphyrin Chemistry, Clay Science Room: 9-446 TEL: +81-42-677-2839 e-mail: [email protected] Tamao ISHIDA Associate Professor/Ph. D. Catalysis Chemsitry Room: 9-447 TEL:+8142-677-2845 e-mail: [email protected] Tetsuya SHIMADA Assistant Prof. / Ph.D. Physical Chemistry, Spectroscopy Room: 9-445 TEL: +81-42-677-1111 (Ext.4897) e-mail: [email protected] Visiting researcher 4 Doctor’s course 4 Master’s course 11 Bachelor 8
■Outlines of the Research Our group challenges to control photochemical reactions such as electron and energy transfer, by controlling the orientation and alignment of dyes on the inorganic surfaces. Recently, organic/inorganic hybrids composed of porphyrins and layered materials have been the subject of intensive investigations to explore their novel properties and functionalities. We found out that a precise matching of distances between the negatively charged sites on the clay mineral layers and that between the positively charged sites in the dye molecule is one of the most important factors to determine the structure of the clay–dye complex. We have termed this the “Size-Matching Rule” Our goal is finding out a new methodology to control molecular assembly structure and realizing functionalized photochemical reaction systems such as an artificial light harvesting system. 1. Research on Artificial light harvesting system Shinsuke TAKAGI, Tetsuya SHIMADA The quantitative excited energy transfer reaction between cationic porphyrins on an anionic clay surface was successfully achieved. The efficiency reached up to ca. 100% owing to the “Size- Matching Rule” that is our original technique. It was revealed that the important factors for the efficient energy transfer reaction are (i) suppression of the self-quenching between adjacent dyes, and (ii) suppression of the segregated adsorption structure of two kinds of dyes on the clay surface. These findings indicate that the clay/porphyrin complexes are promising and prospective candidates to be used for construction of an efficient artificial light-harvesting system. Especially when phthalocyanine was used as energy acceptor, light harvesting type energy transfer was realized. In addition to these, hydrogen evlution systems using sunlight as an energy source has been developed. Especially, photochemical hydrogen and hydroperoxide formation were examined as an energy related subject this year.
Fig. 1. Artificial light harvesting model on the nanosheet. 2. Research on Novel Methodology to Control the Adsorption Structure of Dyes on the Clay Surface Shinsuke TAKAGI, Tetsuya SHIMADA Saponite-type clays that have different cation exchange capacities were successfully synthesized by hydrothermal synthesis. The structure and properties were analyzed by X-ray diffraction, X-ray fluorescence, 27Al NMR, FT-IR, thermogravimetric and differential thermal analysis, atomic force microscopy, and cation exchange capacity measurement. The intercharge distances on the synthetic saponite (SS) surfaces were calculated to be 0.8-1.9 nm on the basis of a hexagonal array. The complex formation behavior between SS and cationic porphyrins was examined. It turns out that the average intermolecular distance between porphyrin molecules on the SS surface can be controlled, depending on the charge density of the SS. The adsorption behavior of porphyrin on the SS surface can be rationally understood by the previously reported “size-matching rule”. This methodology using host-guest interaction can realize a unique adsorption structure control of the porphyrin molecule on the SS surface, where the gap distance between guest porphyrin molecules is rather large. These findings will be highly valuable to construct photochemical reaction systems such as energy transfer in the complexes. In this year, the glass substrate was examined as a novel host material to control the nano-structure of dye assembly.
Fig. 2. An example of our methodology to control the adsorption structure of dyes on the clay surface by using a suitable clay species.
Fig. 3. Adsorption of protein on nanosheets and formation of apoprotein.. 3. Surface – Fixation Induced Emission on the nanosheets Shinsuke TAKAGI, Tetsuya SHIMADA We investigated the fluorescence enhancement behavior of AIE (Aggregation Induced Emission) – active dyes on the clay nanosheet. Judging from their adsorption observation on the clay in water, the factor for the fluorescence enhancement is turned
21
Reports from Research Groups
out not to be AIE, but is to be Surface - Fixation Induced Emission (S - FIE) mechanism. While the effect of AIE depended on the molecular structure of dye in water-dioxane, S - FIE worked even for the dye that has bulky substituent. In this year, not only fluorescence but also phosphorescence was examined as a photochemical behavior. As a result, the enhancement of phosphorescence on clay surface was found put.
Fig. 4. Surface – Induced Emission on the nanosheets. Left: without nanosheet, Right: with nanosheet.. 4. Research on Novel Hybrid Complex of Semiconductor Nano-Sheet and Dye Shinsuke TAKAGI, Tetsuya SHIMADA A semiconductor nano-sheet was focused as our new research target in addition to the "insulator" clay nano-sheet. We expected we effectively extend our distinctive research about clay-dye hybridization methodology in order to create new materials with good electron transfer property for artificial photosynthesis system. We synthesized a novel TiO2 nano-sheet (TNS) and characterized it in detail. We observed adsorption behavior of porphyrin dyes on the TNS and photochemical interaction between the dyes and the TNS.
Fig. 5. Electron injection from Dye to semiconductor nanosheet. 5. Research on Gold Nanoparticle-Catalyzed Organic Reactions Tamao, ISHIDA Nanosheet materals, such as titania nanosheet (TNS) and clay (Sumecton SA, SSA), are regarded as potential supports for metal nanoparticles because of high surface area and ordered anioninc charges on the surfaces. In this year gold nanoparticles (Au NPs) were deposited on TNS and SSA by deposition-reduction method using Au(en)2Cl3 as a precursor. Catalytic activities of Au/TNS and Au/SSA were evaluated by aerobic oxidation of 4-hydroxybenzyl alcohol. Yields of 4-hydroxybenzaldehyde were calculated to be 24 and 60% for Au/TNS and Au/SSA, respectively. Although larger Au NPs were deposited on SSA, Au/SSA showed higher catalytic activity than did Au/TNS. Mean diameters of Au NPs on TNS and SSA were estimated to be 1.7 and 6.7 nm, respectively, by transmission electron microscopy. These findings will contribute to devlop new Au catalysts using nanosheet materials. Hydroxyapatite (HAP) supported Au catalysts have been known to show inverse strong metal-support interaction (SMSI)
in which Au NPs are covered by HAP under oxidative conditions, reported by J. Wang et al. Au atoms at the perimeter interface became cationic under inverse SMSI. Therefore, Au/HAPs seem to be a promising candidate as soft Lewis acid catalysts for alkene activation. Au/HAPs were prepared under oxidative and reductive conditions and were abbreviated as Au/HAP_O2 and Au/HAP_H2, respectively. Although the mean diameters of Au NPs were almost similar (ca. 2 nm), Au/HAP_O2 exhibited higher catalytic activity for alkene isomerization reation than did Au/HAP_H2. This result suggests that the electronic interaction between Au and HAP thin layer of Au/HAP_O2 with SMSI enhaces the soft Lewis acidity, resulting in high catalytic activity.
■Papers with Peer Review 1. Which Type of Clay Minerals Fix Cesium Ion Effectively?
-Cavity-Charge Matching Effect-, T. Yamamoto, T. Takigawa, T. Fujimura, T. Shimada, T. Ishida, H. Inoue, S. Takagi, Phys. Chem. Chem. Phys., 21, 9352-9356 (2019).
2. Reversed Micelles Formed by Polyfluorinated Surfactant II; the Properties of Core Water Phase in Reversed Micelle, S. Takagi, K. Arakawa, T. Shimada, H. Inoue, Bull. Chem. Soc. Jpn., 92, 1200-1204 (2019).
3. Factors for the emission enhancement of dimidium in specific media such as in DNA and on a clay surface, R. Nakazato, K. Sano, H. Ichihara, T. Ishida, T. Shimada, S. Takagi, Phys. Chem. Chem. Phys., 21, 22732-22739 (2019). Selected as “Cover paper”
4. Effect of clay surface on aldehyde-diol equilibrium, K. Arakawa, R. Nakazato, T. Shimada, T. Ishida, M. Eguchi, S. Takagi, Tetrahedron Lett., 60, 150986-150989 (2019).
5. Pd-catalyzed decarbonylation of furfural: Elucidation of support effect on Pd size and catalytic activity using in-situ XAFS, T. Ishida, T. Honma, K. Nakada, H. Murayama, T. Mamba, K. Kume, Y. Izawa, M. Utsunomiya, M. Tokunaga, J. Catal., 374, 320–327 (2019).
6. CO Oxidation over Au/ZnO: Unprecedented Change of the Reaction Mechanism at Low Temperature Caused by a Different O2 Activation Process, T. Fujita, T. Ishida, K. Shibamoto, T. Honma, H. Ohashi, T. Murayama, M. Haruta, ACS Catal., 9, 8364–8372 (2019).
7. Oxidative esterification of aliphatic aldehydes and alcohols with ethanol over gold nanoparticle catalysts in batch and continuous flow reactors, A. Taketoshi, T. Ishida, T. Murayama, T. Honma, M. Haruta, Appl. Catal. A: Gen., 585, 117169 (2019).
8. Imporatance of Size and Contact Structure of Gold Nanoparticles for the Genesis of Unique Catalytic Processes, T. Ishida, T. Murayama, A. Taketoshi, M. Haruta, Chem. Rev., 120, 464–525 (2020). “Inside cover“
9. CO2 Reduction to Methanol on Au/CeO2 Catalysts: Mechanistic Insights from De-Activation and SSITKA Measurements, A. Rezvani, A. M. Abdel-Mageed, T. Ishida, T. Murayama, M. Parlinska-Wojtan, R. J. Behm, ACS Catal., in press.
■Review articles and books 1. Gold Nanoparticles for Oxidation Reactions: Critical Role
of Supports and Au Particle Size, T. Ishida, A. Taketoshi, M. Haruta, Topics in Organometallic Chemistry, “Nanoparticles in Catalysis”, Springer, S. Kobayashi, Ed., in press (2020).
22
Reports from Research Groups
2. Tuning emission properties by dye encapsulation into layered silicates, Y. Ishida, S. Takagi, Springer, “Dyes and Photoactive Molecules in Microporous Systems”, (Virginia Martínez-Martínez, Ed.), in press. See the annual report in Japanese (6 articles)
■Academic Meeting *International 1. Anti-inflammatory effect of metal oxide supported Au
catalysts, T. Ishida, Ausdarc-YTU Symposium on Gold Catalysis 2019, Yantai (China), September, 2019 (Invited).
2. Evaluation of organic-inorganic complexes for hydrogen evolution on clay nanosheets, S. Nagaoka, Y. Ohsaki, M. Kumasaka, T. Shimada, T. Ishida, S. Takagi, The 4th International Symposium on Hydrogen Energy‒based Society, Tokyo (Japan), August, 2019.
3. Novel oxidation reaction sensitized by Sn(IV)Porphyrin aiming at artificial photosynthesis, Y. Ohsaki, H. Tachibana, H. Inoue, T. Shimada, S. Takagi, The 4th International Symposium on Hydrogen Energy‒based Society, Tokyo (Japan), August, 2019.
4. Photochemical properties of water-soluble porphyrin on titania nanosheets aiming at artificial photosynthesis, J. Hara, T. Shimada, T. Ishihda, S. Takagi, The 4th International Symposium on Hydrogen Energy‒based Society, Tokyo (Japan), August, 2019.
5. Adsorption behavior and photochemical property of divalent cationic porphyrin on titania nanosheet, S. Tominaga, K. Sano, T. Shimada, T. Ishida, S. Takagi, The 4th International Symposium on Hydrogen Energy‒based Society, Tokyo (Japan), August, 2019.
6. Selective Catalytic Oxidation of NH3 with High N2 Selectivity over Au/Nb2O5, M. Lin, B. An, N. Niimi, Y. Jikihara, T. Nakayama, T. Takei, T. Shishido, T. Ishida, The 4th International Symposium on Hydrogen Energy‒ based Society, Tokyo (Japan), August, 2019.
7. Effect of the deposition of gold to Nb2O5 for photocatalytic oxidation of 5-hydroxymethylfurfural, C. Mochizuki, T. Shishido, T. Ishida, H. Masatake, T. Murayama, The 4th International Symposium on Hydrogen Energy‒ based Society, Tokyo (Japan), August, 2019.
8. Effects of the size of nanoparticulate gold and their support on selective oxidation of furfural to furoic acid, C. Mochizuki, M. Lin, A. Taketoshi, T. Ishida, M. Haruta, T. Murayama, The 8th Asia-Pacific Congress on Catalysis, Bangkok (Thailand), August, 2019.
9. Selective catalytic oxidation of ammonia using nanoparticulate noble metal deposited on Nb2O5, B. An, M. Lin, N. Niimi, Y. Jikihara, T. Nakayama, T. Ishida, M. Haruta, T. Murayama, The 8th Asia-Pacific Congress on Catalysis, Bangkok (Thailand), August, 2019.
10. Mutual Redox Conversion of NAD+ and NADH by Gold Catalysts, J.-i. Nishigaki, T. Ishida, M. Haruta, The 8th Asia-Pacific Congress on Catalysis, Bangkok (Thailand), August, 2019.
11. Efficient removal of ammonia by using niobium oxide supported gold catalyst with high nitrogen selectivity, M. Lin, B. An, Y. Fukui, Y. Jikihara, T. Nakayama, T. Takei, T. Shishido, T. Ishida, M. Haruta, T. Murayama, The 8th
Asia-Pacific Congress on Catalysis, Bangkok (Thailand), August, 2019.
12. Selective Catalytic Oxidation of NH3 by using Au/Nb2O5, The 10th National Conference on Environmental Chemistry, M. Lin, B. An, Y. Fukui, Y. Jikihara, T. Nakayama, T. Takei, T. Shishido, T. Ishida, M. Haruta, T. Murayama, The 10th National Conference on Environmental Chemistry, Tianjin (China), August, 2019.
13. Effect of the deposition of gold nanoparticle on Nb2O5 for photocatalytic selective oxidation of 5-hydroxymethylfurfural, C. Mochizuki, T. Shishido, T. Ishida, H. Masatake, T. Murayama, Ausdarc-YTU Symposium on Gold Catalysis 2019, Yantai (China), September, 2019.
14. High catalytic activity for CO oxidation below room temperature over Au/Ta2O5, M. Lin, C. Mochizuki, B. An, Y. Inomata, T. Ishida, M. Haruta, T. Murayama, Ausdarc-YTU Symposium on Gold Catalysis 2019, Yantai (China), September, 2019.
15. Role of acid sites in selective catalytic oxidation of NH3 with high N2 selectivity, M. Lin, B. An, Y. Fukui, Y. Jikihara, T. Nakayama, T. Takei, T. Shishido, T. Ishida, M. Haruta, T. Murayama, 9th East Asia Joint Symposium on Environmental Catalysis and Eco-materials, Yancheng (China), November, 2019.
16. Synthesis and Identification of Titanium Oxide Nanoparticle for Molecular Catalyst Sensitized Artificial Photosynthesis Systems, K. Sano, F. Kuttassery, A. Yamakata, B. Ohtani, T. Shimada, H. Tachibana, T. Ishida, S. Takagi, H. Inoue, The 3rd International Conference on Solar Fuels (ISF-3)and International Conference on Artificial Photosynthesis2019 (ICARP2019), Hiroshima (Japan), November, 2019.
17. Emission enhancement of dyes on the inorganic nanosheets, S. Takagi, K. Arakawa, Y. Ishida, T. Ishida, T. Shimada, The 18th Asian Chemical Congress (18th ACC) and The 20th General Assembly of the Federation of Asian Chemical Societies (FACS), Taipei (Taiwan), December, 2019.
18. The Flat Effect of Clay Surface on the Aldehyde-diol Equilibrium, K. Arakawa, T. Ishida, T. Shimada, S. Takagi, The 18th Asian Chemical Congress (18th ACC) and The 20th General Assembly of the Federation of Asian Chemical Societies (FACS), Taipei (Taiwan), December, 2019.
*Domestic See the annual report in Japanese (28 articles)
■Patents See the annual report in Japanese (1 articles)
■Awards 1. The Best Presentation Award for Students, Annual
Meeting on Photochemistry 2019, Yugo HIRADE (M1), September, 2019.
2. Excellent Poster Awards, The 9th CSJ Chemistry Festa, Keito SANO (D1), October, 2019.
3. Sustainable Energy and Fuels (SEF) Award, The 3rd International Conference on Solar Fuels and International Conference on Artificial Photosynthesis2019, Keito SANO (D1), November, 2019.
4. Poster Presentation Awards for Students, The 3rd International Conference on Solar Fuels and International
23
Reports from Research Groups
Conference on Artificial Photosynthesis2019, Keito SANO (D1), November, 2019.
24
Reports from Research Groups
Uchiyama Laboratory
■Members
Katsumi UCHIYAMA
Professor / Dr. Pharmacol.
Analytical Chemistry, Nano/Micro Chemical Fabrication,
Micro Droplet
room: 9-339 TEL: +81-42-677-1111 Ext.4877
e-mail: [email protected]
Hizuru NAKAJIMA
Associate Prof. / Dr.Eng.
Analytical Chemistry, Micro-TAS, Chromatography,
Electrophoresis, Chemical sensor, Bio sensor
room: 9-343 TEL: +81-42-677-1111 Ext.4882
e-mail: nakajima-hizuru @tmu.ac.jp
Shungo KATO
Associate Prof. / Dr.Eng.
Atmospheric Chemistry, Analytical Chemistry, Geochemistry
room: 9-338 TEL: +81-42-677-1111 Ext.4875
e-mail: shungo @tmu.ac.jp
Sifeng MAO
Assistant Prof. / Dr.Eng
Analytical Chemistry, Micro-TAS
room: 9-344 TEL: +81-42-677-1111 Ext.4883
e-mail: maosifeng @tmu.ac.jp
Hidetaka NORITOMI
Assistant Prof. / Dr.Eng.
Enzyme Technology, Nanomaterial,Bioprocess
room: 9-148 TEL: +81-42-677-1111 Ext.4838
e-mail: noritomi @tmu.ac.jp
Sueo KAGAWA
Tech. Assistant
room: 9-290 TEL: +81-42-677-1111 Ext.4872
e-mail: kagawa @tmu.ac.jp
Haruko MIYAMOTO
Tech. Assistant
room: 9-291 TEL: +81-42-677-1111 Ext.4873
e-mail: miyamoto-haruko @jmj.tmu.ac.jp
Doctor’s course -2
Master’s course -11
Bachelor 4 -8
Dissertion Ph.D. supporting by JSPS-1(Tsinghua University)
■Outlines of the Research
1. Development of Small Droplets and Applications
Katsumi UCHIYAMA, Sifeng MAO
Monodispersive micro liquid droplets not only act as ultra
small reaction place with unique characteristics but also enhance
fluorescence intensity of surrounding media. We utilized inkjet,
which is widely used for the inkjet printer, micro dispensing tool
for analytical chemistry and many other fields, as a generation
tool for monodispersive liquid dorplets. In this study we have
developed on-line digital PCR system, new sample introduction
method for capillary electrophoresis, dispensing system for ultra
small amount of liquid for enzyme linked immune sorbent assay,
generation of mono-dispersive polymer particles for drug
delivery system.
1-1 Development of on-line digital PCR system
At first, a certain number of mono-dispersive droplets with
PCR mixture and target DNA were ejected into oil phase.
Concentration of the target DNA was adjusted by diluting until
each droplet has one or zero target DNA. Droplets ejected were
introduced into capillary (id200- 500 μm), then were flown to
the downstream. The capillary was wrapped 30~40 times around
three heating blocks, each of which has same temperatue as PCR
amplification. As a result, PCR amplification was carried out
during the flow through the capillary. Finally, determination was
made by counting fluorescent droplets. We have realized new
on-line digitial PCR system for the first time.
1-2 Droplet enhanced fluorescence, principle and application
We found the the droplet with later refractive index than
surrounding media showed drastic increase of fluorescence
intensity and we named the phenomena DEF (droplet enhanced
fluorescence). The phenomena is based upon the multiple
reflection of incident light at the interface between the droplet
and surrounding media.
We have confirmed the phenomenon by using droplets
ejectedfrom inkjet, then applied the method to ultra sensitive
determination of single strand DNA, ELISA. The method
showed 5~10 times increase in the sensitivity than conventional
methods.
1-3 Application to Capillary electrophoresis
We have developed a new quantitative sample introduction
method for capillary electrophoresis. Inkjet was used for it. And
new method of sample deribatization was developed by using
inkjet. Sample solution and reagent solution was alternately
introduced into the capillary, then these zones were overlapped
for reaction. Finally, delivatized sample was quantitatively
detected.
25
Reports from Research Groups
2. Development of nano/micro chemical pen and its
applications
Katsumi UCHIYAMA, Sifeng MAO
We have developed micro chemical pen, which enabled
position selective micro chemical fabrication on the suface of
material. The chemical pen enabled the fabrication of silver
nano-wires, metal oxide nano-wires and polymer nano wires.
The device will be used for the assembling tool for chemical
machine, fabrication of chemical device and functionalization of
micro machine etcs in the future.
3. Single cell operation
Katsumi UCHIYAMA, Sifeng MAO
One single tumor cell in large tissue was difficult to be
detected when whole tissue was analysed. However, the tumor
would spred to whole tissue in the end. If we can characterize
cell in single cell level, tumor cell will be easily detected and it
leads to the ultra fast diagnosis of tumor and precise study on the
mechanism of metastasis. In this study, we develop tools for the
characterization of single cell, extraction of single cell fluid,
measurement of chemicals exposed from a cell by using the
principle of chemical pen.
4. Development of Micro Total Analysis System Using a
Compact Disk-type Microfluidic Device
Hizuru NAKAJIMA
We have developed a flow-based ELISA system using a
microfluidic device. However, many pumps and valves are
required for multiple immunoassays, which affect total size of
the analytical system. In this study, we developed a solution
sending method based on the centrifugal force generated by
rotating a compact disk-type microfluidic device. A portable
fluorescence detection system, electrochemical detection system
and surface plasmon resonance sensor using the compact disk-
type microfluidic device were developed. Since these systems do
not need pumps and valves, these systems would be useful for
on-site analysis, such as environmental monitoring, food safety
testing and point-of-care testing.
5. Development of Portable ELISA System Using Pipette
Tips
Hizuru NAKAJIMA
Enzyme-linked immunosorbent assay (ELISA) is an
immunological assay commonly used to measure antibodies,
antigens, proteins and glycoproteins in biological samples.
However, the conventional ELISA method relatively needs a
long analysis time and many expensive reagents. In addition,
commercially available microplate readers are large-size and
very expensive. Therefore, it is not possible to measure
biological samples and environmental samples in the field by
ELISA. To overcome these drawbacks, we developed an ELISA
method using pipette tips (PT-ELISA) and the palm-sized
fluorescence detector for PT-ELISA. This PT-ELISA system was
successfully used in the determination of IgA in human saliva, a
marker of stress.
6. Development of Portable Genetic Testing System Based on
LAMP
Hizuru NAKAJIMA
A genetic amplification method using polymerase chain
reaction (PCR) is commonly used in the genetic test. However,
the PCR method is not suitable for on-site genetic test since the
method needs large-sized and expensive assay devices such as a
thermal cycler, an electrophoresis equipment and an absorption
/ fluorescence detector. To overcome these drawbacks, a portable
genetic testing system based on LAMP was developed using
LEDs, photodiodes a transparent glass heater and so on. The
genetic testing system was successfully used in the variety
identification of rice.
7. Development of Multichannel ISFET Sensor for
Measuring pH Distribution of Interstitial Water in
Marine Sediment
Hizuru NAKAJIMA
Recentry, marine acidification is progressing with increasing
the concentration of CO2 in atmosphere. Since the marine
acidification causes the dissolution of sandy soil in coral reef
area, the effect of ocean acidification on marine organisms living
in there is apprehended. Therefore, the measurement of pH
distribution of interstitial water in marine sediment is important
task for evaluating the effect of marine acidification on
ecosystem. In general, the pH value of interstitial water in marine
sediment is measured by diver using the pH meter with glass
electrode. However, the measurement work is very hard, the
glass electrode is fragile, and the pH distribution of interstitial
water could not be measured at same time. To overcome these
drawbacks, a novel multichannel ISFET sensor using Ta2O5 as
an ion sensitive membrane was developed for measureing the pH
distribution of interstitial water in marine sediment.
26
Reports from Research Groups
8. Measurements of VOCs at urban and suburban sites
Shungo KATO
Volatile Organic Compounds (VOCs) were observed at
uburban site (Minamiosawa, Koto-ku, Yokohama). Emission
sources, contribution to ozone formation of each VOC were
estimated.
9. Atmospheric trace species measurements at remote sites
Shungo KATO
Atmospheric carbon monoxide, ozone, and various volatile
organic compounds were continuously observed at remote
sites: cape Hedo in Okinawa, Suzu in Ishikawa.
10. Measurements of atmospheric pollutants at mountain
sites
Shungo KATO
Carbon monoxide, ozone, and sulferdioxide were observed at
summit of Mt. Fuji during summer. There was no influence from
local pollution source and typical air at remote site during
summer was observed. Plume from volcano was observed at Mt.
Fuji. Realtime measurement of gas at the top of Mt. Fuji during
winter without commercial electric power was donducted with
low power gase sensor and LPWA ELTRES (SONY).
11. Atmospheric trace gas measurements using small gas
sensor
Shungo KATO
Atmospheric trace gases and PM2.5 were measeured by
small gas sensors at urban area and clean remote site at the top
of Mt. Fuji. Also, portable system working by battely was
constructed.
12. Hydrogen measurement in ambient aire
Shungo KATO
Gas chromatgrapy/Redection gas detector system was
constructed for low level hydrogen measuremtns. Atmospheric
hydrogen concentration in suburban, urban, and remote sites
were observed.
13. Application of biochar to stress tolerance of proteins
Hidetaka NORITOMI
To reduce greenhouse gas emissions, biochar was prepared
from forestry residues, which are carbon neutral, and was used
as a protein carrier. We found that biochar imparts high heat
stress tolerance and organic solvent stress tolerance to proteins.
This result would be expected to the applications to
bioprocesses such as bioreactors, biosensors, and biofuel cells.
■Papers with Peer Review
1. Syed Niaz Ali Shah, Xiangnan Dou, Mashooq Khan,
Katsumi Uchiyama, Jin-Ming Lin
N-doped carbon dots/H2O2 chemiluminescence system for
selective detection of Fe2+ ion in environmental samples
Talanta, 196, 370–375, (2019)
2. Tsuguhiro Kaneko, Yue Sun, Hizuru Nakajima, Katsumi
Uchiyama, Hulie Zeng
Droplet Sensitized Fluorescence Detection for Enzyme-
Linked Immune Sorbent Assays on Microwell Plate
Anal. Chem. 91(9), 5685-5689, (2019)
3. Haifeng Lin, Sifeng Mao, Hulie Zeng, Yong Zhang, Masato
Kawaguchi, Yumi Tanaka, Jin-Ming Lin, Katsumi Uchiyama
Selective Fabrication of Nanowires with High Aspect Ratios
Using a Diffusion Mixing Reaction System for Applications
in Temperature Sensing
Anal. Chem. 91(11), 7346-7352, (2019)
4. Hidetaka Noritomi, Ryotaro Kai, Nobuyuki Endo, Satoru
Kato, Katsumi Uchiyama
Thermal Stabilization of HEWL by Adsorption on Biochar
Journal of Materials Science Research, 8(4), 30-36, (2019)
5. A. Yamakawa, A. Takami, Y. Takeda, S. Kato, and Y. Kajii,
Investigation of Mercury Emission Sources Using Hg
Isotopic Compositions of Atmospheric Mercury at the Cape
Hedo Atmosphere and Aerosol Monitoring Station
(CHAAMS), Japan,
Environmental Science: Processes & Impacts, 21, 809-818,
(2019)
6. R. Wada, Y. Sadanaga, S. Kato, N. Katsumi, H. Okochi, Y.
Iwamoto, K. Miura, H. Kobayashi, M. Kamogawa, J.
Matsumoto, S. Yonemura, Y. Matsumi, M. Kajino, S.
Hatakeyama,
Ground-based observation of lightning-induced nitrogen
oxides at a mountaintop in free troposphere,
Journal of Atmospheric Chemistry, 76(2), 133-150, (2019)
7. Kohji Marumoto, Noriyuki Suzuki, Yasuyuki Shibata, Akinori
Takeuchi, Akinori Takami, Norio Fukuzaki, Kazuaki
Kawamoto, Akira Mizohata, Shungo Kato, Takashi
Yamamoto, Jingyang Chen, Tatsuya Hattori, Hiromitsu
Nagasaka, Mitsugu Saito,
Long-term observation of atmospheric speciated mercury
during 2007-2018 at Cape Hedo, Okinawa, Japan,
Atmosphere, 10, 362, (2019)
8. Momoka Yoshizue, Yoko Iwamoto, Kouji Adachi, Shungo
Kato, Siyi Sun, Kazuhiko Miura, Mitsuo Uematsu,
Individual particle analysis of marine aerosols collected
during the North-South transect cruise in the Pacific Ocean
and its marginal seas,
Journal of Oceanography, 75, 513-524, (2019)
9. Kojiro Shimda, Masayuki Nohchi, Taichi Sugiyama, Kaori
Miura, Akinori Takami, Kei Sato, Xuan Chen, Shungo Kato,
Yoshizumi Kajii, Fan Meng, Shiro Hatakeyama,
Degradation of PAHs during long range transport based on
simultaneous measurements at Tuoji Island, China, and at
Fukue Island and Cape Hedo, Japan,
Environmental Pollution, 260, 113906, (2020)
See the annual report in Japanese (1 articles)
■Invited Lectures
1. Katsumi Uchiyama
Possible application of push-pull nozzle system for single
cell analyses and manipulation
The Second Symposium for Cell Analysis on
Micro/Nanofluidics, Xijiao Hotel Beijing, Beijing, China
2. Katsumi Uchiyama
Selective Fabrication of Nanowires with High Aspect Ratios
27
Reports from Research Groups
Using a Diffusion Mixing Reaction System for Applications
in Temperature Sensing
2019 China-Japan-Korea Symposium on Analytical Science
( 2019CJK ) , Kyung Hee University (Global Campus)
Yongin, Korea
3. Katsumi Uchiyama
Analytical chemistry in Japan
the 18th Beijing Conference and Exhibition on Instrumental
Analysis (BCEIA 2019), China National Convention Center,
Beijing, China
4. Katsumi Uchiyama
Push-pull nozzle system for the biochemical study
the 18th Beijing Conference and Exhibition on Instrumental
Analysis (BCEIA 2019), China National Convention Center,
Beijing, China
5. Katsumi Uchiyama
Droplet enhanced fluorescence and itsa application to bio-
analysis
the 18th Beijing Conference and Exhibition on Instrumental
Analysis (BCEIA 2019), China National Convention Center,
Beijing, China
■Academic Meeting
*International
1. Hidetaka Noritomi, Ryotaro Kai, Nobuyuki Endo, Satoru
Kato, Katsumi Uchiyama
Thermal Stabilization of Enzymes by Adsorption on Biochar
OKINAWA COLLOIDS 2019(the 70th Anniversary of the
Divisional Meeting of Division of Colloid and Surface
Chemistry), Bankoku Shinryoukan, OKINAWA
*Domestic
See the annual report in Japanese (16articles)
■Books
1. Hidetaka Noritomi
Application of biochar to enzyme carrier for stress tolerance
of enzymes, Biochar-An Imperative Amendment for Soil and
the Environment (ISBN: 978-1-83881-987-3), Ed by Vikas
Abrol, InTech, London, United Kingdom, Chapter 5, pp.75-
95 (2019)
See the annual report in Japanese (1 book)
■Awards
28
Reports from Research Groups
Shishido Laboratory
■Members
Tetsuya Shishido
Professor /Dr. Eng.
Catalyst Science, Surface chemistry, Solid acid-base, Selective
oxidation, in-situ observation
room:9-551 TEL: +81-42-677-2852 (Ext. 4961)
e-mail: [email protected]
Hiroki Miura
Assistant Professor /Dr. Eng.
Catalysis Science, Solid acid-base, Organic chemistry,
Organometallic chemistry
room:9-550 TEL: +81-42-677-2851 (Ext. 4962)
e-mail: [email protected]
Doctor’s course -3
Master’s course -18
Bachelor 4 -7
■Outlines of the Research
1. One-pod synthesis of lactic acid from glycerol by hydrid
catalysis of solid acid-Pt nanoparticles
Lactic acid is an important compound used as various chemicals
such as foods and pharmaceuticals. Due to excess formation of
glycerol as a by-product during biodiesel production, the method
for selective conversion of glycerol to lactic acid is strongly
desired. In this study, we investigated one-step synthesis of lactic
acid from glycerol and found that Pt catalyst supported on Nb2O5
was remarkably effective. This reaction is consisted of two kinds
of reactions, ie, oxidative of glycerol to trioses and subsequent
isomerization to lactic acid. In this catalytic reaction, the
Pt/Nb2O5 functioned as "hybrid catalysts" in which Pt
nanoparticles and Nb2O5 promoted the oxidation and
isomerization, respectively.
2. Silylation of aryl chlorides by bimetallic catalysis of
palladium and gold on alloy nanoparticles
Supported palladium–gold alloy-catalyzed cross-coupling of
aryl chlorides and hydrosilanes enabled the selective formation
of aryl–silicon bonds. Whereas a monometallic palladium
catalyst predominantly promoted the hydrodechlorination of aryl
chlorides and gold nanoparticles showed no catalytic activity,
gold-rich palladium–gold alloy nanoparticles efficiently
catalyzed the title reaction to give arylsilanes with high
selectivity. A wide array of aryl chlorides and hydrosilanes
participated in the heterogeneously-catalyzed reaction to furnish
the corresponding arylsilanes. A detailed mechanistic
investigation revealed that palladium and gold atoms on the
surface of alloy nanoparticles independently functioned as active
sites for the formation of aryl nucleophiles and silyl electrophiles,
respectively, which indicates that palladium and gold atoms on
alloy nanoparticles work together to enable the selective
formation of aryl–silicon bonds.
3. Brønsted acid property of alumina-based mixed-oxides-
supported tungsten oxide
The effect of alumina-based supports on the structure and acid
properties of supported tungsten oxide catalysts was investigated.
WO3/Al2O3–TiO2 (Al2O3/TiO2 = 9, Al–Ti9) showed high activity
for reactions catalyzed by Brønsted acid sites and large Brønsted
acidity. Structural characterization revealed that Brønsted acid
sites on WO3/Al–Ti9 were generated at the boundaries between
domains of amorphous monolayer WO3 and Al2O3–TiO2 support,
and that Al–Ti9 with a high density of Lewis acid and surface
hydroxyl groups resulted in the formation of Brønsted acid sites.
These results suggested that a high density of Lewis acid sites
and surface hydroxyl groups are important factors to form
amorphous WO3 monolayer domains and to generate Brønsted
acid sites on alumina-based supports.
■Papers with Peer Review
1. “Silylation of Aryl Chlorides by Bimetallic Catalysis of
Palladium and Gold on Alloy Nanoparticles” Miura, H.;
Masaki, Y.; Fukuta, Y.; Shishido, T. Adv. Synth. Catal.
2020, in press.【Selected as a Very Important Publication】 2. “Acid Property of Alumina-Based Mixed Oxides
Supported Tungsten Oxide” Saito, M.; Aihara, T.; Miura,
H.; Shishido, T. Catal. Today 2020, in press.
3. “Importance of the Pd and Surrounding Sites in
Hydrosilylation of Internal Alkynes by Palladium-Gold
Alloy Catalyst” Sadhukhan, T.; Junkaew, A.; Zhao, P.;
Miura, H.; Shishido, T.; Ehara, M. Organometallics 2020,
39, 528–537.【Featured as a Supplementary Cover】
4. “Investigation of the mechanism of the selective
hydrogenolysis of C-O bonds over a Pt/WO3/Al2O3
catalyst” Aihara, T.; Miura, H.; Shishido, T. Catal. Today
2020, in press.
5. “One-pot synthesis of lactic acid from glycerol over Pt/L-
29
Reports from Research Groups
Nb2O5 catalyst under base-free conditions” Shixiang, F.;
Takahashi, K.; Miura, H.; Shishido, T. Fuel Process.
Technol. 2020, 197, 106202
6. “Reductive Cycloisomerization of Diynes by Supported
Palladium Catalysts and Subsequent [4+2] Cycloaddition
Leading to Cyclohexene Derivatives” Miura, H.; Tanaka
Y.; Nakahara, K.; Shishido, T. ChemCatChem 2019, 12,
455–458.
7. “Effect of Perimeter Interface Length between 2D WO3
Monolayer Domain and γ-Al2O3 on Selective
Hydrogenolysis of Glycerol to 1,3-Propanediol” Aihara,
T.; Miura, H.; Shishido, T. Catal. Sci. Technol. 2019, 9,
5359–5367.
8. “Supported Gold-Palladium Alloy Catalysts for Highly
Efficient Hydrogen Storage System based on Ammonium
Bicarbonate/Formate Redox Equilibrium” Nakajima, K.;
Tominaga, M.; Waseda, M.; Miura, H.; Shishido, T. ACS
Sustainable Chem. Eng. 2019, 7, 6522–6530.
9. “The importance of direct reduction in synthesizing highly
active Pt-Sn/SBA-15 for n-butane dehydrogenation” Deng,
L.; Miura, H.; Ohkubo, T.; Shishido, T.; Zheng, W.;
Hosokawa, S.; Teramura, K.; Tanaka, T. Catal. Sci.
Technol. 2019, 9, 947–956. 【Featured as a Front Cover】 10. “Catalysis of Cu Cluster for NO Reduction by CO:
Theoretical Insight into Reaction Mechanism and
Experimental Evidence” Takagi, N.; Ishimura, K.; Miura,
H.; Shishido, T.; Fukuda, R.; Ehara, M.; Sakaki, S.ACS
Omega 2019, 4, 2596–2609.
11. “Role of the Acid Site for Selective Catalytic Oxidation of
NH3 over Au/Nb2O5” Lin, M.; An, Baoxiang; Niimi, N.;
Jikihara, Y.; Nakayama, T.; Honma, T; Takei, T.; Shishido,
T.; Ishida, T.; Haruta, M.; Murayama, T., ACS Catal., 2019,
9, 1753-1756.
■Invited Lectures
1. 124th CatSJ Meeting “Design of Brensted acid sites with
high hydrophobicity and their catalysis toward hydrolysis
of organic molecules” 2019/9/19 Nagasaki University
2. Design of High-Performance Alloy catalysts: Enhancing
Activity and Switching Selectivity by the Incorporation of
Palladium into Gold Nanoparticles,
T. Shishido, (Jan. 4th (Fri)), National Taiwan University,
Taipei, Taiwan.
3. Supported Palladium-Gold Alloy Catalysts for Highly
Efficient Hydrogen Storage System, (Invited Lecture), T.
Shishido, PACCON2020 (Pure and Applied Chemistry
International Conference 2020) (13-14th February 2020),
Bangkok
4. 141th Meeting of the surface finishing society of japan
“Highly efficient hydrogen evolution-storage by PdAu
alloy nanoparticle catalysts” T. Shishido 2020/3/3, Tokyo
Metropolitan University.
5. 100th annual meeting of CSJ “Hydrogen production by
supported alloy nanoparticle catalysts” T. Shishido,
2020/3/22-26, Tokyo University of Science.
■Academic Meeting
*International
1. Selective Catalytic Reduction of NO over Delafossite-type
Oxide
Shengyan Piao, Shinsuke Imai, Hiroki Miura, Tetsuya
Shishido,The 17th Korea-Japan Symposium on Catalysis,
May 20-22, 2019, Jeju, Korea
2. Silylation of aryl chlorides by supported Pd-Au alloy
catalysts
Y. Masaki, H. Miura, T. Shishido, The 1st International
Symposium on Hybrid Catalysis for Enabling Molecular
Synthesis on Demand, May 30-31, 2019, Tokyo, Japan
3. Development of perovskite type catalyst for oxidative
coupling of methane
A. Nishida, H. Miura, T. Shishido, The 8th Asia Pacific
Congress on Catalysis (APCAT-8) August 4-7, 2019,
Bangkok, Thailand
4. One pot conversion of glycerol to lactic acid over
supported platinum catalyst
K. Takahashi, S. Feng, H. Miura, T. Shishido, The 8th
Asia-Pacific Congress on Catalysis (APCAT-8) August 4-
7, 2019, Bangkok, Thailand
5. Acid property of alumina-based mixed oxides supported
tungsten oxide
Mizuki Saito, Hiroki Miura, Tetsuya Shishido, The 8th
Asia-Pacific Congress on Catalysis(APCAT-8), August 4-
7, 2019, Bangkok, Thailand
6. Interconversion between bicarbonate and formate over
supported palladium-gold alloy catalysts
M. Waseda, K. Nakajima, M. Tominaga, H. Miura, T.
Shishido, The eightth Asia Pacific Congress on Catalysis
(APCAT-8) August 4-7, 2019, Bangkok, Thailand
7. [2+2+2] Cycloaddition of Alkynes by Concerted Catalysis
of Adjacent Pd–Au in Alloy Nanoparticles
H. Miura, T. Shishido, 14th European Congress on
Catalysis 2019 (EuropaCat2019), August 18-23, 2019,
Aachen, Germany
8. Selective Silylation of Aryl halides by Supported
Palladium-Gold Alloy Catalysts
Y. Masaki, H. Miura, T. Shishido, 14th European Congress
on Catalysis 2019 (EuropaCat2019), August 18-23, 2019,
Aachen, Germany
9. Kinetic study on reaction mechanism of hydrogenolysis
over Pt/WO3/Al2O3 catalysts
T. Aihara, H. Miura, T. Shishido, EuropaCat2019 August
18–23, 2019, Aachen, Germany
10. Selective CO2 hydrogenation over supported Rh catalysts
J. Suzuki, H. Miura, T. Shishido, 14th European Congress
on Catalysis (EuropaCat 2019, Aachen) August 18-23,
2019, Aachen, Germany
11. Supported Pd-based alloy catalysts for highly efficient
hydrogen storage system based on carbon dioxide/formic
acid cycle
M. Waseda, E. Kawai, H. Miura, T. Shishido, The fourth
International Symposium on Hydrogen Energy-based
Society August 22-23, 2019, Tokyo, Japan
12. Selective catalytic reduction of NO over Cu-Cr/Al2O3
catalysts
Shengyan Piao, Hiroki Miura, Tetsuya Shishido, The 9th
East Asia Joint Symposium on Environmental Catalysis
and Eco-materials, November 5-8, 2019, Yancheng, China
13. Selective catalytic reduction of NO with CO and C3H6
over Rh/HAP
S. Doi, S. Hayashi, H. Miura, T. Shishido, The 9th East
Asia Joint Symposium on Environmental Catalysis and
Eco-materials, November 5-8, 2019, Yancheng, China
*Domestic
See the annual report in Japanese (40 articles)
■Awards
30
Reports from Research Groups
1. Poster Award "Alloying effect of Pd and Au on selective
hydrosilylation of allenes" Suguru Sasaki 121th CatSJ
Meeting (22-23 March 2018, The University of Tokyo).
2. Poster Award "Hydrolytic desilylation of silyl ethers by
Brønsted acid gel catalysts with highly hydrophobic
surface" Syutaro Kameyama 121th CatSJ Meeting (22-23
March 2018, The University of Tokyo).
3. Poster Award ‘‘Structural characterization of supported
PdTe catalysts for oxidative diacetoxylation of olefines”
Yuta Homae 40th summer seminar of junior society of
CatSJ in Hamamatsu, August 3, 2019, Aichi.
4. Best Poster Award “Sillylation of sp2 C-H bonds in
heteroaromatics by supported Au catalysts” Ryuji Hirata
17th catalysts chemistry workshop at Himeji, July 25,
2019, Hyogo
5. Excellent Poster Award ‘‘Sillylation of sp2 C-H bonds in
heteroaromatics by supported Au catalysts” Ryuji Hirata
9th CSJ chemistry festa, Funabori. 23-25 October 2019,
Tower Hall Funabori
6. Excellent Poster Award ‘‘Supported NiAu catalysts
effective for hydrosilaytion of alkynes” Yohei Fukuta 9th
CSJ chemistry festa, Funabori. 23-25 October 2019,
Tower Hall Funabori
7. Catalysis Society of Japan Award for Young Researchers
2019 “Transformation of organic molecules by concerted
catalysis of different elements on the surface of PdAu alloy
nanoparticles” Hiroki Miura, January 6th 2020,
8. Best poster award “Selective catalytic reduction of NO
over Cu-Cr/Al2O3 catalysts”
Shengyan Piao, Hiroki Miura, Tetsuya Shishido, The 9th
East Asia Joint Symposium on Environmental Catalysis
and Eco-materials, November 5-8, 2019 Yancheng, China
9. Best poster award Selective catalytic reduction of NO
with CO and C3H6 over Rh/HAP
S. Doi, S. Hayashi, H. Miura, T. Shishido, The 9th East
Asia Joint Symposium on Environmental Catalysis and
Eco-materials, November 5-8, 2019, Yancheng, China
31
Reports from Research Groups
Shudo Laboratory
■Members Toshio Shudo Professor /Dr. Eng. Energy Engineering, room: 9-455 TEL: +81-42-677-2715 e-mail: [email protected] Doctor’s course -0 Master’s course -3 Bachelor 4 -3
■Outlines of the Research 1. Performance improvement in polymer electrolyte fuel cell, Toshio Shudo Because polymer electrolyte fuel cell has higher energy efficiency and lower power density compared to internal combustion engine, it is important to improve the performance of polymer electrolyte fuel cell. This research investigates the effect of porous metal flow field for even supply of reactants to the whole area of electrodes. 2. Performance improvement in direct methanol fuel cell. Toshio Shudo Direct methanol fuel cell system has higher energy density and lower power density compared to polymer electrolyte fuel cell system. This research investigates the effect of porous metal flow field for enhancing the reactant supply and product removal at the electrodes. 3. Ignition control in homogeneous charge compression ignition combustion. Toshio Shudo Internal combustion engine has higher power density and lower energy efficiency compared to fuel cell system. This research investigates a new combustion system by the compression ignition of homogeneous fuel-air mixture for achieving higher thermal efficiency in internal combustion engines.
■Papers with Peer Review See the annual report in Japanese (2 article)
■Reviews See the annual report in Japanese (2 article)
■Academic Meeting *Domestic See the annual report in Japanese (4 articles)
■Awards See the annual report in Japanese (1 award)
32
Applied Chemistry Colloquium
383th 2019/5/16
Katsuhiko Ariga (National Institute for Materials Science & The
University of Tokyo)
”How do you control molecular machines and nanocars by top-science
instruments or your own hands?”
384th 2019/5/22
Yoichi TOMINAGA (Tokyo University of Agriculture and Technology,
Institute of Engineering, Division of Applied Chemistry)
”Development of Li ion-conductive solid polymers”
385th 2019/7/10
Ziyi Zhong (Guangdong Technion Israel Institute of Technology)
”Heterogeneous catalysts: preparation or synthesis?”
386th 2019/8/27
Kazuo Tanaka (Department of Polymer Chemistry, Graduate School of
Engineering, Kyoto University)
”Development of functional luminescent materials based on non-
luminescent molecules”
387th 2019/9/10
Hiroyasu Furukawa (University of California, Berkeley)
”Design and Synthesis of Metal–Organic Frameworks for Hydrogen
Storage Applications”
388th 2019/9/13
Atsushi Maruyama (Tokyo Institute of Technology: School and Graduate
School of Bioscience and Biotechnology)
”Flexible Polyelectrolyte Complexes for Enhancement and
Development of Biomolecular Functions”
389th 2019/10/16
33
Applied Chemistry Colloquium
Eric Apel (National Center for Atmospheric Research, USA)
”Volatile Organic Compounds and Atmospheric Chemistry”
390th 2019/12/12
Wen-Yueh Yu (National Taiwan University)
”Surface Engineering of Ceria-Based Catalysts forNon-Reductive
Conversion of Carbon Dioxide”
Kevin Chia-Wen Wu (National Taiwan University)
”Water-based Synthesis of Metal-Organic Frameworks (MOFs) for
Energy Applications”
391th 2019/12/21
Sung-Soo Kim (Chungnam National University)
”Thermal and structural stabilities of LixCoO2 cathode for Li secondary
battery studied by a temperature programmed reduction”
34
Annual Report 2019 Published by Tokyo Metropolitan University Faculty of Environmental Sciences Department of Applied Chemistry for Environmental Sciences
April 1, 2019